EP2850681A1 - Method for producing electrode materials - Google Patents

Method for producing electrode materials

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Publication number
EP2850681A1
EP2850681A1 EP13721936.6A EP13721936A EP2850681A1 EP 2850681 A1 EP2850681 A1 EP 2850681A1 EP 13721936 A EP13721936 A EP 13721936A EP 2850681 A1 EP2850681 A1 EP 2850681A1
Authority
EP
European Patent Office
Prior art keywords
iron
compound
lithium
primary particles
water
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP13721936.6A
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German (de)
French (fr)
Other versions
EP2850681B1 (en
Inventor
Bastian Ewald
Ivana KRKLJUS
Jordan Keith Lampert
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Schweiz AG
BASF SE
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BASF Schweiz AG
BASF SE
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Priority to EP13721936.6A priority Critical patent/EP2850681B1/en
Publication of EP2850681A1 publication Critical patent/EP2850681A1/en
Application granted granted Critical
Publication of EP2850681B1 publication Critical patent/EP2850681B1/en
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/45—Phosphates containing plural metal, or metal and ammonium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/37—Phosphates of heavy metals
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a process for the production of electrode materials, which comprises the following steps:
  • (D2) at least one iron source which is different from (D1) and insoluble in water and in which Fe is in the oxidation state zero, +2 or +3,
  • the present invention relates to electrode materials and their use and lithium ion batteries containing electrodes of this material. Preferred embodiments are to be taken from the claims and the description of the invention. Combinations of preferred embodiments are within the scope of the present invention.
  • lithium-containing spinels for example lithium-containing spinels, layered mixed oxides such as, for example, lithiated nickel-manganese-cobalt oxides and lithium-iron oxides.
  • phosphates for example lithium-containing spinels, layered mixed oxides such as, for example, lithiated nickel-manganese-cobalt oxides and lithium-iron oxides.
  • Lithium iron phosphates are of particular interest because they contain no toxic heavy metals and in many cases are very robust against oxidation and water.
  • a disadvantage of lithium iron phosphates may be the comparatively low energy density.
  • a process for producing lithium iron phosphates in the presence of organic solvents for use in lithium ion batteries is disclosed in WO 09/015565.
  • batteries based on lithium iron phosphates are unsatisfactory in some applications in which high peak power is required, for example for cordless screwdrivers with which you want to drill and screw in concrete.
  • Other examples are starters for motor vehicles and motorcycles. It is seen as problematic that the desired rapid discharge is not achieved with lithium-ion batteries based on lithium iron phosphates.
  • the object was to provide a method by which one can produce electrode materials, and allow a fast discharge, so a high peak power, the corresponding batteries. Accordingly, the method defined above was found, hereinafter also referred to as inventive method.
  • stage (a) several of the starting materials, preferably all the starting materials involved, are mixed in several or preferably in one step.
  • vessels for mixing for example, stirred tank and stirred flasks are suitable.
  • the starting material (A) is selected from at least one phosphorus compound, hereinafter also called phosphorus compound (A), selected from phosphine and compounds in which phosphorus in the oxidation state +1 or +3 or +5, for example phosphines having at least one alkyl group or at least an alkoxy group per molecule, phosphorus halides, phosphonic acid, hypophosphorous acid and phosphoric acid.
  • phosphorus compound (A) selected from phosphine and compounds in which phosphorus in the oxidation state +1 or +3 or +5, for example phosphines having at least one alkyl group or at least an alkoxy group per molecule, phosphorus halides, phosphonic acid, hypophosphorous acid and phosphoric acid.
  • Preferred phosphanes are those of the general formula (I) where the variables are chosen as follows:
  • R 1 may be different or the same and is selected from phenyl and preferably C 1 -C 10 -alkyl, cyclic or linear, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, cyclopentyl, iso-amyl, iso-pentyl, n-hexyl, iso-hexyl, cyclohexyl, and 1, 3-dimethylbutyl, preferably n-Ci-C6-alkyl, particularly preferably methyl, Ethyl, n-propyl, isopropyl, and most preferably methyl or ethyl.
  • R 1 may be different or preferably the same and selected from the abovementioned C 1 -C 6 -alkyl radicals.
  • X 1 may be different or the same and is selected from halogen, hydroxyl groups, phenoxy groups and alkoxy groups, preferably of the formula OR 1 , in particular methoxy and
  • halogen is preferably bromine and more preferably chlorine, r, s are selected from integers in the range of zero to three,
  • phosphorus compound (A) is selected from compounds of general formula P (OR 1 ) 3, wherein R 1 may be different or preferably the same and selected from phenyl and C 1 -C 10 -alkyl, more preferably P (OCH 3 ) 3 and P (OC 2 H 5 ) 3 .
  • phosphorus compound (A) is selected from compounds of the general formula wherein R 1 may be different or preferably the same and selected from phenyl and C 1 -C 10 -alkyl, are particularly preferred
  • phosphorus compound (A) is selected from compounds of the general formula wherein R 1 may be different or preferably the same and selected from phenyl and C 1 -C 10 -alkyl, are particularly preferred
  • 0 P (C 6 H 5 ) 3
  • 0 P (CH 3 ) 3
  • 0 P (C 2 H 5 ) 3 .
  • hypophosphorous acid and phosphoric acid can be selected in each case the free acid or corresponding salts, in particular lithium and ammonium salts.
  • phosphoric acid and phosphonic acid can be selected in each case the mononuclear acids H 3 P0 3 or H 3 P0 4 , but also two-, three- or polynuclear acids, for example ⁇ 4 ⁇ 2 ⁇ 7 or polyphosphoric acid.
  • a mixed condensed compound is selected, for example obtainable by condensation of phosphoric acid with phosphorous acid.
  • the starting material (A) two or more phosphorus compounds (A) are selected. In another embodiment of the present invention, exactly one phosphorus compound (A) is chosen.
  • the starting material (B) is selected from at least one lithium compound, also called lithium compound (B), preferably at least one inorganic lithium compound.
  • suitable inorganic lithium compounds are lithium halides, for example lithium chloride, furthermore lithium sulfate, lithium acetate, LiOH, Li 2 CO 3 , L 12 O and LiNO 3 ; preferred are L12SC, LiOH, Li2C0 3 , L12O and LiN0 3 .
  • lithium compound can contain water of crystallization, for example LiOH ⁇ H2O.
  • the phosphorus compound (A) and lithium compound (B) are each selected as L1H 2 PO 2, lithium phosphate, lithium orthophosphate, Lithium metaphosphate, lithium phosphonate, lithium phosphite, lithium hydrogen phosphate or lithium dihydrogen phosphate, ie, lithium phosphate, lithium phosphonate, lithium phosphite or lithium (di) hydrogen phosphate may each serve simultaneously as phosphorus compound (A) and as lithium compound (B).
  • the starting material (C) is selected from at least one carbon source, also called carbon source (C), which may be a separate carbon source or at least one phosphorus compound (A) or lithium compound (B).
  • carbon source (C) is to be understood as meaning that a further starting material is used which is selected from elemental carbon in a modification which conducts the electric current or a compound which is used in the thermal treatment in step (b) is decomposed into carbon and different from phosphorus compound (A) and lithium compound (B).
  • carbon source (C) for example, carbon in a modification that conducts the electric current is suitable, for example, carbon black, graphite, graphene, carbon nanotubes or activated carbon.
  • graphite are not only mineral and synthetic graphite, but also expanded graphite and intercalated graphite.
  • Carbon black may, for example, be selected from lampblack, furnace black, flame black, thermal black, acetylene black, carbon black and furnace carbon black.
  • Carbon black may contain impurities, for example hydrocarbons, in particular aromatic hydrocarbons, or oxygen-containing compounds or oxygen-containing groups, for example OH groups.
  • sulfur or iron-containing impurities in carbon black are possible.
  • modified carbon blacks or modified graphites are used, for example those carbon blacks or graphites which have hydroxyl groups, epoxy groups, keto groups or carboxyl groups.
  • further compounds of carbon are suitable, which are decomposed to carbon during the thermal treatment in step (c).
  • synthetic and natural polymers unmodified or modified, are suitable.
  • synthetic polymers are polyolefins, for example polyethylene and polypropylene, furthermore polyacrylonitrile, polybutadiene, polystyrene, and copolymers of at least two comonomers selected from ethylene, propylene, styrene, (meth) acrylonitrile and 1,3-butadiene.
  • polyisoprene and polyacrylates are suitable. Particularly preferred is polyacrylonitrile.
  • polyacrylonitrile is understood to mean not only polyacrylonitrile homopolymers, but also copolymers of acrylonitrile with 1,3-butadiene or styrene. Preference is given to polyacrylonitrile homopolymers.
  • polyethylene is understood to mean not only homo-polyethylene, but also copolymers of ethylene which contain at least 50 mol% of ethylene in copolymerized form and up to 50 mol% of at least one further comonomer, for example Olefins such as propylene, butylene (1-butene), 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-pentene, also isobutene, vinyl aromatics such as styrene, further
  • Olefins such as propylene, butylene (1-butene), 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-pentene, also isobutene, vinyl aromatics such as styrene, further
  • Polyethylene may be HDPE or LDPE.
  • polypropylene is understood to mean not only homo-polypropylene but also copolymers of propylene which contain at least 50 mol% of propylene polymerized and up to 50 mol% of at least one further comonomer, for example ethylene and ⁇ -propylene.
  • Olefins such as butylene, 1-hexene, 1-octene, 1-decene, 1-dodecene and 1-pentene.
  • Polypropylene is preferably isotactic or substantially isotactic polypropylene.
  • polystyrene is understood to mean not only homopolymers of styrene, but also copolymers with acrylonitrile, 1,3-butadiene, (meth) acrylic acid, C 1 -C 10 -alkyl esters of (meth) acrylic acid, divinylbenzene, in particular 1, 3. Divinylbenzene, 1, 2-diphenylethylene and a-methylstyrene.
  • Another suitable synthetic polymer is polyvinyl alcohol.
  • Suitable natural polymers as carbon source (C) are, for example, starch, cellulose, alginates (eg agar agar, furthermore pectins, gum arabic, oligo and polysaccharides, guar gum and locust bean gum as well as amylose and amylopectin.
  • alginates eg agar agar, furthermore pectins, gum arabic, oligo and polysaccharides, guar gum and locust bean gum as well as amylose and amylopectin.
  • modified natural polymers are understood to mean by polymer-analogous reaction modified natural polymers. Suitable polymer-analogous reactions are, in particular, the esterification and the etherification. Preferred examples of modified natural polymers are methanol-etherified starch, acetylated starch and acetyl cellulose, furthermore phosphated and sulfated starch.
  • carbides are suitable as the carbon source (C), preferably covalent carbides, for example iron carbide FesC.
  • low volatility low molecular weight organic compounds are suitable as carbon source (C). Particularly suitable compounds are those which do not evaporate at temperatures in the range from 350 to 1200 ° C., but decompose, for example as solids. or in the melt.
  • dicarboxylic acids for example phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, tartaric acid, citric acid, pyruvic acid, furthermore sugars, for example monosaccharides having 3 to 7 carbon atoms per molecule (trioses, tetroses, pentoses, hexoses, heptoses) and condensates of monosaccharides such as, for example Di-, tri- and oligosaccharides, in particular lactose, glucose and fructose, as well as sugar alcohols and sugar acids, for example aldonic acids, ketoaldonic acids, uronic acids and aldaric acids, in particular galactonic acid.
  • dicarboxylic acids for example phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, tartaric acid, citric acid, pyruvic acid
  • sugars for example monosaccharides having 3 to 7 carbon atoms per molecule (
  • low molecular weight organic compounds as carbon source (C) are urea and its less volatile condensates biuret, melamine, melam (N2- (4,6-diamino-1, 3,5-triazin-2-yl) -1, 3, 5-triazine-2,4,6-triamine) and Meiern (1, 3,4,6,7,9,9b-heptaazaphenalene-2,5,8-triamine).
  • carbon sources (C) are salts, preferably iron, ammonium salts and alkali metal salts, more preferably iron, sodium, potassium, ammonium or lithium salts, of organic acids, for example alkanoates, in particular acetates, propionates, butyrates, furthermore lactates , Citrates, tartrates and benzoates.
  • organic acids for example alkanoates, in particular acetates, propionates, butyrates, furthermore lactates , Citrates, tartrates and benzoates.
  • Particularly preferred examples are ammonium acetate, potassium ammonium tartrate, potassium hydrogen tartrate, potassium sodium tartrate, sodium tartrate, sodium hydrogen tartrate, lithium hydrogentate, lithium ammonium tartrate, lithium tartrate, lithium citrate, potassium citrate, sodium citrate, iron acetate, lithium acetate, sodium acetate, potassium acetate, lithium lactate, ammonium lactate, sodium lactate and potassium lactate.
  • the carbon source (C) and phosphorus compound (A) used are an organic phosphorus compound, for example trimethyl phosphate, triethyl phosphite, triphenyl phosphine and triphenyl phosphine oxide (CeH.sub.3 PO).
  • the respective carbon source (C) and lithium compound (B) are selected from lithium acetate, lithium lactate or lithium hydrogen tartrate, i.
  • Lithium compound (B) Lithium acetate, lithium lactate or lithium hydrogen tartrate can each serve simultaneously as carbon source (C).
  • At least two iron compounds or iron and at least one iron compound (D1) are selected. You choose
  • iron compound (D1) also referred to as “iron compound (D1)” or “component (D1)” for short, and (D2) at least one iron source which is different from (D1) and insoluble in water and in which Fe is in the oxidation state zero, +2 or +3.
  • iron source (D2) may be selected from iron or preferably at least one water-insoluble iron compound in which Fe is in the oxidation state zero, +2 or +3, also referred to as “iron compound (D2)” or “component (D2)". designated.
  • oxidation state +2 or +3 means the oxidation state in which Fe is present in the relevant iron compound (D1) or iron compound (D2) at the beginning of the mixing after step (a).
  • Water-soluble in connection with iron compound (D1) is understood to mean that the solubility in demineralized water at a pH of 7 and 20 ° C. is at least 0.1 g Fe ions / l, preferably in the range from 1 to 500 g / l.
  • water-insoluble in connection with iron compound (D2) that the solubility in demineralized water at a pH of 7 and 20 ° C is less than 0.1 g Fe ions / l, for example 10 "10 bis 0.01 g / l.
  • Iron compound (D1) and iron compound (D2) are preferably inorganic iron compounds.
  • iron compound (D1) from anhydrous and hydrous iron compounds, such as the hydrates.
  • Hydrates are to be understood as meaning not only monohydrates but also other hydrates, for example, in the case of iron (II) oxalate, also the dihydrate, in the case of iron (II) chloride also the tetrahydrate and in the case of iron (III) nitrate also the nonahydrate.
  • water-soluble iron compound (D1) is selected from ammonium iron (II) sulfate, ammonium iron (III) sulfate, ammonium iron (II) citrate, ammonium iron (III) citrate, iron (II) bromide, iron (III ) bromide, iron (II) fluoride, iron (III) fluoride, iron (II) ethoxide, iron (II) gluconate, iron (II) nitrate, iron (III) nitrate, iron (II) acetate, FeSO 4 , Fe 2 ( S0 4 ) 3, iron (II) oxalate, iron (II) citrate, iron (III) citrate, iron (III) acetylacetonate, iron (II) lactate, iron (III) lactate and iron chloride, for example FeC and hydrous iron (III )chloride.
  • water-insoluble iron compound (D2) is selected from Fe (OH) 3 , FeOOH, Fe 2 O 3 -aq, FeO, Fe 2 O 3 , Fe 3 O 4 , FeS, Iron (II) phosphate
  • iron (Fe 3 (PO 4 ) 2), iron (III) phosphate (FePO 4 ), iron (II) pyrophosphate, iron (III) pyrophosphate, iron carbide, iron phosphide, iron (II) phosphonate, iron (III) phosphonate, and iron carbonate, are Trains t forthcoming Fe (OH) 3, FeOOH, Fe2Ü 3, Fe 3 0 4, iron phosphate and iron (II) carbonate.
  • iron compound (D1) and (D2) can each be selected from anhydrous and hydrous iron compounds, for example the hydrates. Hydrates should not only be understood as meaning monohydrates but also other hydrates, for example in the case of iron (II) phosphate also octahydrate.
  • water-insoluble iron compound (D2) is selected from iron pentacarbonyl.
  • Starting material (D1) can be used, for example, as an aqueous solution or as a powder, for example with average particle diameters (D50) in the range from 10 to 750 nm, preferably in the range from 25 to 500 nm.
  • Starting material (D2) can be used, for example, as an aqueous suspension or as powder, for example with average primary particle diameters (D50) in the range of 10 to 750 nm, preferably in the range of 25 to 500 nm.
  • starting material (D2) may be in the form of agglomerates.
  • the carbon source (C) and iron compound (D1) are each selected from iron acetate, iron citrate, iron gluconate, iron ethoxide, or ammonium iron citrate, i. the iron compound (D1) iron (II) acetate, iron (II) acetylacetonate, iron (II) citrate, iron (II) lactate, iron (III) lactate, ammonium iron (II) citrate, iron (III) acetate, iron (III) acetylacetonate, iron (III) citrate or ammonium iron (III) citrate can simultaneously serve as carbon source (C).
  • the carbon source (C) and iron compound (D2) are each chosen to be iron carbide.
  • lithium iron citrate i. Lithium iron citrate can in each case simultaneously serve as iron compound (D1), carbon source (C) and as lithium compound (B).
  • iron compound (D1) and iron compound (D2) are selected in a molar ratio of from 1: 1 to 1: 9, preferably to 15: 85, the molar ratio to Fe in iron compound (D1) and iron compound (D2 ) (or elemental iron) is related.
  • an iron compound (D1) and two iron compounds (D2) are used.
  • an iron compound (D2) and two iron compounds (D1) are used.
  • two phosphorus compounds (A), a lithium compound (B), a carbon source (C), an iron compound (D1) and an iron compound (D2) are used.
  • two phosphorus compounds (A), one lithium compound (B), two carbon sources (C), an iron compound (D1) and an iron compound (D2) are used.
  • two phosphorus compounds (A), one lithium compound (B), two carbon sources (C), an iron compound (D1) and an iron compound (D2) are used, and iron compound (D1) is a salt of an organic compound is and serves as one of the carbon sources (C).
  • one or more reducing compounds may be used in step (a), for example one or more reducing agents (E) may be employed.
  • This embodiment is preferred if at least one iron compound (D1) or (D2) is used in which Fe is present in the oxidation state +3.
  • suitable reducing compounds are those phosphorus compounds (A) in which P is in the +3 or +1 oxidation state, in particular phosphorous acid (H3PO3), hypophosphorous acid (H3PO2) and their respective ammonium and lithium salts, and also esters, for example Ci-Cio-alkyl esters.
  • reducing agent (E) elemental iron is also suitable.
  • reducing agent (E) it is possible to use gaseous, liquid or solid substances which, under the conditions of step (a) or (b), convert iron, if necessary, into the oxidation state +2.
  • a solid reducing agent (E) is selected from a metal, for example nickel or manganese, or a metal hydride.
  • gaseous reducing agent (E) can be used for example hydrogen, carbon monoxide, ammonia and / or methane. If it is desired to use one or more gaseous reducing agents (E), it is preferred to use the gaseous reducing agent (E) in step (b), which is further explained below.
  • Suitable reducing agents (E) are metallic iron and iron pentacarbonyl. In another embodiment of the present invention, no reducing agents (E) are used.
  • step (a) in step (a), the proportions of iron compounds (D1 and (D2), phosphorus compound (s) (A) and lithium compound (s) (B) are chosen so that the desired stoichiometry of an iron compound
  • step (a) the proportions of iron compounds (D1 and (D2), phosphorus compound (s) (A) and lithium Select compound (s) (B) such that the stoichiometry yields, for example, Li 3 Fe 2 (PO 4 ) 3, Li 2 Fe 2 (PO 4 ) 2, Li 4 Fe (PO 4 ) 2 or Li 2 FeP 2 O 7 or in particular LiFePO 4 .
  • starting material (F) it is possible to use at least one further metal compound in which the one or more metals are different from iron, in short also called metal compound (F).
  • metal compound (F) it is preferable to use one or more metals from the first period of the transition metals as the metal.
  • metal compound (F) from compounds of Ti, V, Cr, Mn, Co, Ni, Mg, Al, Nb, W, Mo, Cu and Zn, in particular compounds of Sc, Ti, V, Mn, Ni and Co.
  • metal compound (F) from oxides, hydroxides, carbonates and sulfates of metals of the first period of the transition metals.
  • Metal compound (F) may be anhydrous or hydrous. Metal cation in metal compound (F) can be present in complexed form, for example as hydrate complex, or uncomplexed.
  • Metal compound (F) can be a salt, for example halide, in particular chloride, furthermore nitrate, carbonate, sulfate, oxide, hydroxide, acetate, citrate, tartrate, oxalate or acetylacetonate, or salts with different anions.
  • salts are selected from oxides, carbonates, hydroxides and nitrates, basic or neutral.
  • Very particularly preferred examples of metal compounds (F) are oxides, hydroxides, carbonates and sulfates.
  • metal compound (F) is selected from fluorides, for example as alkali metal fluoride, especially sodium fluoride.
  • metal compound (F) may act as one or the sole carbon source (C), for example nickel acetate, cobalt acetate,
  • metal compound (F) may act as one or the sole reducing agent (E).
  • reducing agent (E) examples which may be mentioned are manganese (II) acetate, MnCO 3, MnSO 4 , nickel lactate, manganese hydride, nickel hydride, nickel suboxide, nickel carbide, manganese carbide and manganese (II) lactate.
  • the components (A) to (D2) are mixed together in the presence of water.
  • the presence of water is understood in particular to mean that preferably at least 20% by weight, particularly preferably at least 40% by weight, in particular at least 60% by weight of water, based in each case on the total mass of components (A) to (D2 ) and water is used. In most cases not more than 90% by weight of water, based on the total mass of components (A) to (D2) and water, is used. In one variant, water and organic solvent (G) are added.
  • organic solvents are in particular halogen-free organic solvents (G) such as methanol, ethanol, isopropanol or n-hexane, cyclohexane, acetone, ethyl acetate, diethyl ether and diisopropyl ether.
  • G halogen-free organic solvents
  • organic solvent is used with, it is preferably contained in minor amounts.
  • the content of organic solvent is not more than 5% by weight based on the amount of water.
  • the proportions are considerably lower, for example up to 2 wt .-% or 1 wt .-%.
  • the proportion of organic solvent is only in the range of occurring impurities of water.
  • step (a) it is preferred to use water in step (a) but no organic solvents (G).
  • Water of different qualities can be used.
  • purified, preferably demineralized water is used.
  • step (a) can be carried out, for example, by stirring one or more suspensions of the starting materials (A) to (D2) and optionally (E), (F) and (G).
  • the starting materials (A) to (D) and optionally (E) and (F) are intimately mixed together as solids.
  • the starting materials (A) to (D2) and, if appropriate, (E) and (F) and (G) may be kneaded together to form a paste.
  • the mixing in step (a) is carried out at temperatures in the range from zero to 200 ° C, preferably it is carried out at temperatures in the range of room temperature up to 1 10 ° C, particularly preferably up to 80 ° C.
  • the mixing in step (a) is carried out under atmospheric pressure. In other embodiments, the mixing is carried out at elevated pressure, for example at 1, 1 up to 20 bar. In other embodiments, the mixing in step (a) is carried out under reduced pressure, for example at 10 mbar up to 990 mbar.
  • the mixing in step (a) can be carried out over a period in the range of one minute to 12 hours, preferred are 15 minutes to 4 hours, more preferably 20 minutes to 2 hours.
  • the mixing in step (a) is performed in one step.
  • the mixing in step (a) is carried out in two or more stages.
  • water and / or organic solvent are initially added, followed by sequential addition with lithium compound (B), iron compound (D1) and iron compound (D2), phosphorus or phosphorus compound (C), carbon source (B) and optionally with Reducing agent (E) and / or further metal compound (F).
  • Step (a) gives a mixture of at least one phosphorus compound (A), at least one lithium compound (B), at least one carbon source (C), at least one iron compound (D1), at least one iron compound (D2), optionally reducing agent (E) , optionally further metal compound (F), water and optionally organic solvent (G) in pasty form, as a water-containing powder, as a suspension or as a solution.
  • a mixture of step (a) may be dried.
  • drying it is possible, for example, to evaporate water and optionally organic solvent (G), for example by distilling off, freeze-drying, preferably by spray-drying and in particular by spray-drying.
  • organic solvent G
  • the mixture from step (a) is dried, for example with a sputtering dryer.
  • a sputtering dryer for example, atomizing dryers with disc atomizers, with atomized nozzle atomization and those with two-component atomizing, in particular with internally mixing two-component nozzles, are suitable.
  • the mixture of step (a) is spray-dried by means of an at least apparatus which operates to spray at least one spray nozzle, i. one carries out a spray drying or spray drying.
  • the spray drying can be carried out in a spray dryer.
  • Suitable spray dryers are drying towers, for example drying towers with one or more atomizing nozzles and spray dryer with integrated fluidized bed.
  • Particularly preferred nozzles are two-phase nozzles (English: two-phase nozzles), ie nozzles in the interior or at the mouths by means of separate approaches different substances Physical state can be brought intensively mixed.
  • Further examples of suitable nozzles are combination nozzles, for example combinations of binary and pressure nozzles.
  • Hot gas stream or the hot inert gas stream or the hot burner exhaust gases may have a temperature in the range of 170 to 550 ° C, preferably 200 to 350 ° C, in particular 250 to 330 ° C.
  • the mixture is dried within a fraction of a second or within a few seconds to a dry material, which is preferably obtained as a powder.
  • the resulting powder may have a certain residual moisture, for example in the range of 500 ppm to 10 wt .-%, preferably in the range of 1 to 8 wt .-%, particularly preferably in the range of 2 to 6 wt .-%.
  • the starting temperature of the gas stream may be for example in the range 90 to 190 ° C, preferably 1 10 to 170 ° C, in particular 125 to 150 ° C.
  • the temperature of the hot air stream or of the hot inert gas stream or of the hot burner exhaust gases is selected such that it lies above the temperature in step (a).
  • the hot air stream or the hot inert gas stream or the hot burner exhaust gases flow in the direction of the introduced mixture from step (a) (DC method).
  • the hot air stream or hot inert gas stream flows the hot burner exhaust gases in the opposite direction to the introduced mixture from step (a) (countercurrent process).
  • the spraying device is preferably located at the upper part of the spray dryer, in particular the spray tower. Resulting dry material can be separated after the actual spray drying by a separator, such as a cyclone from the hot air stream or hot inert gas or from the hot burner exhaust gases. In another embodiment, incurred dry material after the actual spray drying separated by one or more filters from the hot air flow or hot inert gas or from the hot burner exhaust gases.
  • Dry material can, for example, have an average particle diameter (D50, weight average) in the range from 1 to 50 ⁇ m. It is preferred if the average particle diameter (D99), (determined as volume average) up to 120 ⁇ , more preferably up to 50 ⁇ and most preferably up to 20 ⁇ .
  • D50 weight average
  • D99 volume average
  • step (b) of the process according to the invention the mixture from step (a) or the dry matter is treated thermally, and preferably at temperatures in the range from 350 to 1200 ° C., preferably from 400 to 900 ° C.
  • the thermal treatment in step (b) is carried out in a temperature profile with two to five, preferably with three or four zones, wherein each zone of the temperature profile preferably has a higher temperature than the preceding one.
  • a temperature in the range of 350 to 550 ° C can be set, in a second zone in the range of 450 to 750 ° C, the temperature being higher than in the first zone.
  • you wish to introduce a third zone you can thermally treat in the third zone at 700 to 1200 ° C, but in any case at a temperature higher than in the second zone.
  • the zones can be created, for example, by setting certain heating zones.
  • step (b) If one wishes to carry out step (b) intermittently, one can set a temporal temperature profile, ie. H. For example, it is first treated at 350 to 550 ° C, then at 450 to 750 ° C, the temperature being higher than in the first phase. If you wish to introduce a third phase, you can treat in the third phase at 700 to 1200 ° C, but in any case at a temperature that is higher than in the second phase.
  • a temporal temperature profile ie. H. For example, it is first treated at 350 to 550 ° C, then at 450 to 750 ° C, the temperature being higher than in the first phase.
  • you wish to introduce a third phase you can treat in the third phase at 700 to 1200 ° C, but in any case at a temperature that is higher than in the second phase.
  • the thermal treatment according to step (b) can be carried out, for example, in a rotary kiln, a push-through furnace or RHK (English roller-hearth-kiln), a pendulum reactor, a muffle furnace, a calcination furnace or a quartz ball furnace.
  • the thermal treatment according to step (b) can be carried out, for example, in a weakly oxidizing atmosphere, preferably in an inert or reducing atmosphere.
  • Weakly oxidizing means in the context of the present invention an oxygen-containing nitrogen atmosphere which contains up to 2% by volume of oxygen, preferably up to 1% by volume.
  • step (b) may be carried out over a period of time in the range of 1 minute to 24 hours, preferably in the range of 10 minutes to 3 hours.
  • the inventive method can be carried out without much dust.
  • Materials produced by the process according to the invention are characterized by very good rate capability, ie very good capacity at high discharge rates. They are therefore very suitable for operating devices such as drills and Akkubohrschraubern.
  • Another object of the present invention are electrode materials in particulate form, containing agglomerates of primary particles, wherein the agglomerates contain i.
  • Primary particles of lithiated iron phosphate with olivine structure in short also called “primary particles (i)", wherein the primary particles (i) have an average diameter (D50) in the range of 20 to 250 nm, preferably 50 to 150 nm, ii.
  • Primary particles of lithiated iron phosphate with olivine structure in short also called “primary particle (ii)", wherein the primary particles (ii) have an average diameter (D50) in the range of 300 to 1000, preferably 350 to 750 nm, iii. optionally carbon in electrically conductive modification, also called “carbon (iii)” for short.
  • carbon (iii) can have an average particle diameter (D50) (primary particle diameter) in the range from 1 to 500 nm, preferably in the range from 2 to 100 nm, particularly preferably in the range from 3 to 50 nm, very particularly preferably in the range from 4
  • particle diameter of carbon (iii) in the context of the present invention are preferably given as volume average, determinable for example by XRD analysis and by imaging methods such as SEM / TEM.
  • the average diameter of primary particles (i) and primary particles (ii) can be detected by XRD analysis and by imaging techniques such as SEM / TEM, the diameter of the secondary particles (ii), for example by laser diffraction on dispersions (gaseous or liquid).
  • primary particles (i) and primary particles (ii) are present in agglomerates in a volume ratio (D50) in the range of 1: 9 to 1: 1.
  • the weight ratio of the sum of primary particles (i) and primary particles (ii) to carbon (iii) is in the range from 200: 1 to 5: 1, preferably 100: 1 to 10: 1, particularly preferably 100: 1, 5 to 20: 1.
  • Carbon (iii) may be present in the pores of secondary particles (agglomerates) of primary particles (i) and primary particles (ii) or in the form of particles containing agglomerates of primary particles (i) and primary particles (ii) punctiform or one or more particles of carbon (iii) can contact.
  • carbon (iii) can be present as a coating of agglomerates of primary particles (i) and primary particles (ii), as a complete coating or as a partial coating.
  • Such an optionally partial coating can also be present, for example, in the interior of agglomerates of primary particles (i) and primary particles (ii), ie in pores.
  • carbon (iii) and agglomerates of primary particles (i) and primary particles (ii) are present next to each other in discrete particles which contact each other punctiformly or not at all.
  • carbon (iii) is present partially as a coating of agglomerates of primary particles (i) and primary particles (ii) as well as in the form of separate particles.
  • agglomerates of primary particles (i) and primary particles (ii) are in the form of particles having an average particle diameter in the range from 1 to 150 ⁇ m (D50). Preference is given to mean particle diameters (D50) of the agglomerates in the range from 1 to 50 ⁇ m, particularly preferably in the range from 1 to 30 ⁇ m, for example determinable by laser diffraction.
  • agglomerates of primary particles (i) and primary particles (ii) are present in the form of particles which have a mean pore diameter in the range of 0.05 ⁇ m to 2 ⁇ m and which can be present in agglomerates.
  • the mean pore diameter can be determined, for example, by mercury porosimetry, for example according to DIN 66133.
  • agglomerates of primary particles (i) and primary particles (ii) are present in the form of particles having an average pore diameter in the range from 0.05 ⁇ m to 2 ⁇ m and a mono- or multimodal course of the intrusion volumes in the range from 100 to 0.001 ⁇ m and preferably have a pronounced maximum in the range between 10 ⁇ m and 1 ⁇ m, preferably two pronounced maxima, one each between 10 and 1 and between 1 and 0.1 ⁇ m.
  • Carbon (iii) is, for example, carbon black, graphite, graphene, carbon nanotubes, expanded graphites, intercalated graphites or activated carbon.
  • carbon (iii) is carbon black.
  • Carbon black may, for example, be selected from lampblack, furnace black, flame black, thermal black, acetylene black, carbon black and furnace carbon black.
  • Carbon black may contain impurities, for example hydrocarbons, in particular aromatic hydrocarbons, or oxygen-containing compounds or oxygen-containing groups, for example OH groups, epoxide groups, carbonyl groups and / or carboxyl groups.
  • impurities for example hydrocarbons, in particular aromatic hydrocarbons, or oxygen-containing compounds or oxygen-containing groups, for example OH groups, epoxide groups, carbonyl groups and / or carboxyl groups.
  • sulfur or iron-containing impurities in carbon black are possible.
  • carbon (iii) is partially oxidized carbon black.
  • Partially oxidized carbon black also referred to as activated carbon black, contains oxygen-containing groups such as, for example, OH groups, epoxide groups, carbonyl groups and / or carboxyl groups.
  • carbon (iii) is carbon nanotubes.
  • Carbon nanotubes carbon nanotubes, short CNT or English carbon nanotubes
  • SW CNT single-walled carbon nanotubes
  • MW CNT multi-walled carbon nanotubes
  • carbon nanotubes have a diameter in the range of 0.4 to 50 nm, preferably 1 to 25 nm.
  • carbon nanotubes have a length in the range of 10 nm to 1 mm, preferably 100 nm to 500 nm.
  • Carbon nanotubes can be prepared by methods known per se. For example, one can use a volatile carbon-containing compound such as methane or carbon monoxide, acetylene or ethylene, or a mixture of volatile carbon-containing compounds such as synthesis gas in the presence of one or more reducing agents such as hydrogen and / or another gas such as nitrogen decompose. Another suitable gas mixture is a mixture of carbon mono- xid with ethylene.
  • Suitable decomposition temperatures are, for example, in the range from 400 to 1000.degree. C., preferably from 500 to 800.degree.
  • Suitable pressure conditions for the decomposition are, for example, in the range of atmospheric pressure to 100 bar, preferably up to 10 bar.
  • Single- or multi-walled carbon nanotubes can be obtained, for example, by decomposition of carbon-containing compounds in the arc, in the presence or absence of a decomposition catalyst.
  • the decomposition of volatile carbon-containing compound or carbon-containing compounds in the presence of a decomposition catalyst for example Fe, Co or preferably Ni.
  • graphene is understood as meaning almost ideal or ideally two-dimensional hexagonal carbon crystals, which are constructed analogously to individual graphite layers. They can be one C-atom layer thick or only a few, for example 2 to 5 C-atom layers. Graphene can be prepared by exfoliation or by delamination of graphite.
  • intercalated graphites are understood to mean not completely delaminated graphites which contain other atoms, ions or compounds intercalated between the hexagonal C atom layers.
  • alkali metal ions, SO 3, nitrate or acetate can be incorporated.
  • the production of intercalated graphites are known, see for example Rüdorff, Z. anorg. Gen. Chem. 1938, 238 (1), 1.
  • Intercalated graphites are e.g. represented by thermal expansion of graphite.
  • Expanded graphites can be obtained, for example, by expansion of intercalated graphites, see e.g. McAllister et al. Chem. Mater. 2007, 19, 4396-4404.
  • the electrode materials according to the invention are those which have been prepared by the method according to the invention described above.
  • electrode material according to the invention additionally contains at least one binder (iv), for example a polymeric binder.
  • binder for example a polymeric binder.
  • Suitable binders (iv) are preferably selected from organic (co) polymers.
  • Suitable (co) polymers, ie homopolymers or copolymers, can be selected, for example, from anionic, catalytic or free-radical (co) polymerization
  • (Co) polymers in particular of polyethylene, polyacrylonitrile, polybutadiene, polystyrene, and copolymers of at least two comonomers selected from ethylene, propylene, styrene,
  • (Meth) acrylonitrile and 1, 3-butadiene In addition, polypropylene is suitable. Furthermore, polyisoprene and polyacrylates are suitable. Particularly preferred is polyacrylonitrile. In the context of the present invention, polyacrylonitrile is understood to mean not only polyacrylonitrile homopolymers, but also copolymers of acrylonitrile with 1,3-butadiene or styrene. Preference is given to polyacrylonitrile homopolymers.
  • polyethylene is understood to mean not only homo-polyethylene, but also copolymers of ethylene which contain at least 50 mol% of ethylene and up to 50 mol% of at least one further comonomer, for example ⁇ -olefins such as Propylene, butylene (1-butene), 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-pentene, furthermore isobutene, vinylaromatics such as styrene, for example
  • ⁇ -olefins such as Propylene, butylene (1-butene), 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-pentene, furthermore isobutene, vinylaromatics such as styrene, for example
  • Polyethylene may be HDPE or LDPE.
  • polypropylene is understood to mean not only homo-polypropylene but also copolymers of propylene which contain at least 50 mol% of propylene polymerized and up to 50 mol% of at least one further comonomer, for example ethylene and ⁇ -propylene.
  • Olefins such as butylene, 1-hexene, 1-octene, 1-decene, 1-dodecene and 1-pentene.
  • Polypropylene is preferably isotactic or substantially isotactic polypropylene.
  • polystyrene is understood to mean not only homopolymers of styrene, but also copolymers with acrylonitrile, 1,3-butadiene, (meth) acrylic acid, C 1 -C 10 -alkyl esters of (meth) acrylic acid, divinylbenzene, in particular 1, 3. Divinylbenzene, 1, 2-diphenylethylene and a-methylstyrene.
  • Another preferred binder (iv) is polybutadiene.
  • Other suitable binders (iv) are selected from polyethylene oxide (PEO), cellulose, carboxymethylcellulose, polyimides and polyvinyl alcohol.
  • binders (iv) are selected from those (co) polymers which have an average molecular weight M w in the range from 50,000 to 1,000,000 g / mol, preferably up to 500,000 g / mol.
  • Binders (iv) may be crosslinked or uncrosslinked (co) polymers.
  • binder (iv) is selected from halogenated (co) polymers, in particular from fluorinated (co) polymers.
  • Halogenated or fluorinated (co) polymers are understood as meaning those (co) polymers which contain at least one (co) monomer in copolymerized form, which contains at least one or at least one fluorine atom per molecule, preferably at least two halogen atoms or at least two fluorine atoms per molecule.
  • Examples are polyvinyl chloride, polyvinylidene chloride, polytetrafluoroethylene, polyvinylidene fluoride (PVdF), tetrafluoroethylene-hexafluoropropylene copolymers, vinylidene fluoride-hexafluoropropylene copolymers (PVdF-HFP), vinylidene fluoride-tetrafluoroethylene copolymers, perfluoroalkylvinyl ether copolymers, ethylene-tetrafluoroethylene copolymers, vinylidene fluoride copolymers. Chlorotrifluoroethylene copolymers and ethylene-chlorofluoroethylene copolymers.
  • Suitable binders (iv) are in particular polyvinyl alcohol and halogenated (co) polymers, for example polyvinyl chloride or polyvinylidene chloride, in particular fluorinated (co) polymers such as polyvinyl fluoride and in particular polyvinylidene fluoride and polytetrafluoroethylene.
  • electrode material according to the invention contains:
  • Inventive electrode materials can be used well for the production of electrochemical cells. For example, they can be processed into pastes with good rheological properties.
  • Another object of the present invention are electrochemical cells prepared using at least one electrode according to the invention.
  • Another object of the present invention are electrochemical cells containing at least one electrode according to the invention.
  • Another aspect of the present invention is an electrode containing agglomerates of primary particles (i) and primary particles (ii), carbon (iii) and at least one binder (iv).
  • the geometry of electrodes according to the invention can be chosen within wide limits. It is preferred to design electrodes according to the invention in thin films, for example in films with a thickness in the range from 10 ⁇ m to 250 ⁇ m, preferably from 20 to 130 ⁇ m.
  • electrodes according to the invention comprise a foil, for example a metal foil, in particular an aluminum foil, or a polythene foil.
  • merfolie for example, a polyester film, which may be untreated or siliconized. The film is coated on one or both sides with inventive electrode material.
  • Another aspect of the present invention is the use of electrode materials according to the invention for the production of electrodes of lithium-ion batteries.
  • Another aspect of the present invention is a method of making electrodes using electrode materials of the invention.
  • Electrochemical cells according to the invention definitely serve as cathodes in electrochemical cells according to the invention.
  • Electrochemical cells according to the invention contain a counterelectrode which is defined as an anode in the context of the present invention and which can be, for example, a carbon anode, in particular a graphite anode, a lithium anode, a silicon anode or a lithium titanate anode.
  • Electrochemical cells according to the invention may be, for example, batteries or accumulators.
  • Electrochemical cells according to the invention can comprise, in addition to the anode and the electrode according to the invention, further constituents, for example conductive salt, nonaqueous solvent, separator, current conductor, for example of a metal or an alloy, furthermore cable connections and housing.
  • further constituents for example conductive salt, nonaqueous solvent, separator, current conductor, for example of a metal or an alloy, furthermore cable connections and housing.
  • electrical cells according to the invention contain at least one non-aqueous solvent, which may be liquid or solid at room temperature, preferably selected from polymers, cyclic or non-cyclic ethers, cyclic and non-cyclic acetals and cyclic or non-cyclic organic Carbonates.
  • non-aqueous solvent which may be liquid or solid at room temperature, preferably selected from polymers, cyclic or non-cyclic ethers, cyclic and non-cyclic acetals and cyclic or non-cyclic organic Carbonates.
  • suitable polymers are in particular polyalkylene glycols, preferably P0IV-C1-C4-alkylene glycols and in particular polyethylene glycols.
  • Polyethylene glycols may contain up to 20 mol% of one or more C 1 -C 4 -alkylene glycols in copolymerized form.
  • polyalkylene glycols are polyalkylene glycols double capped with methyl or ethyl.
  • the molecular weight M w of suitable polyalkylene glycols and especially of suitable polyethylene glycols may be at least 400 g / mol.
  • the molecular weight M w of suitable polyalkylene glycols and in particular of suitable polyethylene glycols may be up to 5,000,000 g / mol, preferably up to 2,000,000 g / mol
  • suitable non-cyclic ethers are, for example, diisopropyl ether, di-n-butyl ether, 1, 2-dimethoxyethane, 1, 2-diethoxyethane, preference is 1, 2-dimethoxyethane.
  • Suitable cyclic ethers are tetrahydrofuran and 1,4-dioxane.
  • non-cyclic acetals are, for example, dimethoxymethane, diethoxymethane, 1,1-dimethoxyethane and 1,1-diethoxyethane.
  • Suitable cyclic acetals are 1, 3-dioxane and in particular 1, 3-dioxolane.
  • suitable non-cyclic organic carbonates are dimethyl carbonate, ethyl methyl carbonate and diethyl carbonate.
  • Suitable cyclic organic carbonates are compounds of the general formulas (II) and (III)
  • R 3 , R 4 and R 5 may be identical or different and selected from hydrogen and C 1 -C 4 -alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec. Butyl and tert-butyl, preferably R 4 and R 5 are not both tert-butyl.
  • R 3 is methyl and R 4 and R 5 are each hydrogen or R 5 , R 3 and R 4 are each hydrogen.
  • Another preferred cyclic organic carbonate is vinylene carbonate, formula (IV).
  • the solvent (s) are preferably used in the so-called anhydrous state, ie with a water content in the range from 1 ppm to 0.1% by weight, determinable for example by Karl Fischer titration.
  • Inventive electrochemical cells also contain at least one conductive salt. Suitable conductive salts are in particular lithium salts.
  • lithium salts examples include LiPF 6, LiBF 4, UCIO4, LiAsFe, L1CF3SO3, LiC (CnF 2n + IS02) 3, lithium imides such as LiN (CnF 2 n + IS02) 2, where n is an integer ranging from 1 to 20; LiN (SO 2 F) 2, Li 2 SiF 6, LiSbF 6, LiAICU, and salts of the general formula (C n F 2n + i SO 2) mYLi, where m is defined as follows:
  • m 2 when Y is selected from nitrogen and phosphorus
  • m 3 when Y is selected from carbon and silicon.
  • Preferred conducting salts are selected from LiC (CF 3 SO 2 ) 3 , LiN (CF 3 SO 2 ) 2 , LiPF 6 , LiBF 4 ,
  • L1CIO4 and particularly preferred are LiPF6 and LiN (CFsSO2) 2.
  • electrochemical cells according to the invention contain one or more separators, by means of which the electrodes are mechanically separated.
  • Suitable separators are polymer films, in particular porous polymer films, which are unreactive with respect to metallic lithium.
  • Particularly suitable materials for separators are polyolefins, in particular film-shaped porous polyethylene and film-shaped porous polypropylene.
  • Polyolefin separators especially polyethylene or polypropylene, may have a porosity in the range of 35 to 45%. Suitable pore diameters are for example in the range from 30 to 500 nm.
  • separators may be selected from inorganic particle filled PET webs.
  • Such separators may have a porosity in the range of 40 to 55%. Suitable pore diameters are for example in the range of 80 to 750 nm.
  • Electrochemical cells according to the invention furthermore contain a housing which can have any shape, for example cuboidal or the shape of a cylindrical disk.
  • a metal foil developed as a bag is used as the housing.
  • Inventive electrochemical cells can be combined with each other, for example in series or in parallel. Series connection is preferred.
  • Another object of the present invention is the use of electrochemical cells according to the invention in devices, in particular in mobile devices.
  • mobile devices are vehicles, such as automobiles, two-wheeled vehicles, aircraft or watercraft. witnesses like boats or ships.
  • Other examples of mobile devices are those that you move yourself, for example computers, especially laptops, telephones or electrical tools, for example in the field of construction, in particular drills, cordless screwdrivers or cordless tackers.
  • lithium-ion batteries comprising at least one electrode, containing at least one electrode material according to the invention. Accordingly, another aspect of the present invention is lithium-ion batteries containing at least one electrode according to the invention.
  • Lithium-ion batteries of the invention are used in devices that require high-power, and thus fast-discharge, batteries.
  • Examples of such devices are drills, cordless screwdrivers or cordless tackers or starters for cold starting of vehicles, such as automobiles or motorcycles.
  • Lithium-ion batteries according to the invention have a high peak power. The discharge rate preferably exceeds 5C for at least a short time. Lithium-ion batteries according to the invention can also be discharged quickly, if desired. For example, they can be discharged at 10C within 12 minutes, preferably within 10 minutes, with only a slightly decreasing capacity.
  • step (a.1) the following starting materials were used:
  • step (a.1) The solution from step (a.1) was sprayed in a spray tower by program under air.
  • the hot air flow at the entrance had a temperature of 305 ° C, at the exit still 121 ° C.
  • the dryer was operated with 450 kg / h of drying gas and 33 kg / h of nozzle gas (atomizing gas) with an atomization pressure of 3.5 bar.
  • a yellow free-flowing powder with a residual moisture content of 8% was obtained. It was in the form of particles whose diameter (D50) was 22.6 ⁇ . SEM images showed spherical agglomerates of yellow powder internally held by the organic component lactose.
  • 60 g of the yellow powder obtained as described above was thermally treated in a 2 liter quartz rotary kiln under an atmosphere of IS.
  • the 2 liter quartz spin ball rotated at a speed of 10 rpm. First, it was heated to 700 ° C within 60 minutes. Then calcined for 60 minutes at 700 ° C. Then allowed to cool to room temperature. It was sieved (mesh 50 ⁇ ) and received an inventive electrode material EM.1, which looked black and was obtained in powder form.
  • BET 26 m 2 / g.
  • the tamped density of the sieve fraction ⁇ 32 ⁇ was 0.73 g / ml.
  • step (a.2) the following starting materials were used:
  • step (a.2) The solution from step (a.2) was sprayed in a spray tower by program under air.
  • the hot air flow at the entrance had a temperature of 305 ° C, at the exit still 121 ° C.
  • the dryer was operated with 450 kg / h of drying gas and 33 kg / h of nozzle gas (sputtering gas) with an atomization pressure of 3.5 bar.
  • a yellow free-flowing powder with a residual moisture content of 8% was obtained. It was in the form of particles whose diameter (D50) was 18.3 ⁇ .
  • SEM images showed spherical agglomerates of yellow powder held together by the organic component mannitol.
  • 60 g of the yellow powder obtained as described above was thermally treated in a 2 liter quartz rotary kiln under an atmosphere of IS.
  • the 2 liter quartz spin ball rotated at a speed of 10 rpm. First, it was heated to 700 ° C within 60 minutes. Then calcined for 60 minutes at 700 ° C. Then allowed to cool to room temperature. It sieved (mesh 50 ⁇ ) and received an electrode material V-EM.2, which looked black and was obtained in powder form. BET: 9.1 m 2 / g.
  • the tamped density of the sieve fraction ⁇ 32 ⁇ was 1, 01 g / ml.
  • step (a.3) the following starting materials were used:
  • Anchor stirrer submitted and heated to 53 ° C. Subsequently, the LiOH ⁇ H2O (B.1) was dissolved therein and then the iron compound (D2.1) was added. Thereafter, phosphorus compounds (A.1) and (A.2) were added. The temperature rose to 69 ° C. Thereafter, the carbon sources (C.1) and (C.3) were added. The mixture was stirred at 70 ° C. over a period of fourteen hours (pH: 4.6). A yellow suspension was obtained.
  • step (a.3) The solution from step (a.3) was sprayed under air in a spray tower according to the program.
  • the hot air flow at the entrance had a temperature of 305 ° C, at the exit still 121 ° C.
  • the dryer was operated with 450 kg / h of drying gas and 33 kg / h of nozzle gas (sputtering gas) with an atomization pressure of 3.5 bar.
  • 60 g of the yellow powder obtained as described above was thermally treated in a 2 liter quartz rotary kiln under an atmosphere of IS.
  • the 2 liter quartz spin ball rotated at a speed of 10 rpm. First, it was heated to 700 ° C within 60 minutes. Then calcined for 60 minutes at 700 ° C. Then allowed to cool to room temperature. It sieved (mesh 50 ⁇ ) and received an electrode material V-EM.3, which looked black and was obtained in powder form. BET: 28 m 2 / g.
  • the tamped density of the sieve fraction ⁇ 32 ⁇ was 0.81 g / ml.
  • step (a.4) the following starting materials were used:
  • Anchor stirrer submitted and heated to 44 ° C. Subsequently, the LiOH ⁇ H2O (B.1) was dissolved therein and then the iron compound (D2.1) was added. Thereafter, phosphorus compounds (A.1) and (A.2) were added. The temperature rose to 62 ° C. Thereafter, the carbon sources (C.1) and (C.3) were added. The mixture was stirred at 70 ° C. over a period of fourteen hours (pH: 4.6). A yellow suspension was obtained.
  • step (a.4) was diluted with 4 l of water and then sprayed in a spray tower under program in air.
  • the hot air flow at the entrance had a temperature of 305 ° C, at the exit still 121 ° C.
  • the dryer was operated with 450 kg / h of drying gas and 33 kg / h of nozzle gas (sputtering gas) with an atomization pressure of 3.5 bar.
  • a yellow free-flowing powder with a residual moisture content of 8% was obtained. It was in the form of particles whose diameter (D50) was 6.3 ⁇ and (D90) 19.4 ⁇ . SEM images showed spherical agglomerates of the yellow powder held together by the organic component starch / lactose.
  • 60 g of the yellow powder obtained as described above was thermally treated in a 2 liter quartz rotary kiln under an atmosphere of IS.
  • the 2 liter quartz spin ball rotated at a speed of 10 rpm.
  • BET 9.1 m 2 / g.
  • the tamped density of the sieve fraction ⁇ 32 ⁇ was 1, 01 g / ml.
  • step (a.5) the following starting materials were used:
  • the pH of the solution from step (a.5) was adjusted to 5.0 with ammonia water. Thereafter, the resulting solution was sprayed in a spray tower by program under air.
  • the hot air flow at the entrance had a temperature of 305 ° C, at the exit still 121 ° C.
  • the dryer was operated with 450 kg / h of drying gas and 33 kg / h of nozzle gas (sputtering gas) with an atomization pressure of 3.5 bar.
  • a yellow free-flowing powder with a residual moisture content of 8% was obtained. It was in the form of particles whose diameter (D50) was 18.3 ⁇ . SEM images showed spherical agglomerates of yellow powder held together by the organic component polyvinyl alcohol.
  • Step (b.5) 60 g of the yellow powder obtained as described above were dissolved in a 2 l
  • step (a.6) the following starting materials were used:
  • the solution from step (a.6) was diluted with 8 l of water. Thereafter, the pH of the thus diluted solution from step (a.6) was adjusted to 5.0 with ammonia water. Thereafter, the resulting solution was sprayed in a spray tower by program under air.
  • the hot air flow had a temperature of 305 ° C at the entrance, and 121 ° C at the exit.
  • the dryer was operated with 450 kg / h of drying gas and 33 kg / h of nozzle gas (sputtering gas) with an atomization pressure of 3.5 bar.
  • a yellow free-flowing powder with a residual moisture content of 8% was obtained. It was in the form of particles whose diameter (D50) was 14 ⁇ . SEM images showed spherical agglomerates of yellow powder held together by the organic component stearic acid.
  • 60 g of the yellow powder obtained as described above was thermally treated in a 2 liter quartz rotary kiln under an atmosphere of IS.
  • the 2 liter quartz spin ball rotated at a speed of 10 rpm. First, it was heated to 700 ° C within 60 minutes. Then calcined for 60 minutes at 700 ° C. Thereafter, the mixture was allowed to cool to room temperature.
  • the tamped density of the sieve fraction ⁇ 32 ⁇ was 0.95 g / ml.
  • step (a.7) the following starting materials were used:
  • step (a.7) The solution from step (a.7) was diluted with 8 l of water. Thereafter, the resulting solution was sprayed in a spray tower by program under air.
  • the hot air flow at the entrance had a temperature of 305 ° C, at the exit still 121 ° C.
  • the dryer was operated with 450 kg / h of drying gas and 33 kg / h of nozzle gas (sputtering gas) with an atomization pressure of 3.5 bar.
  • a yellow free-flowing powder with a residual moisture content of 8% was obtained. It was in the form of particles whose diameter (D50) was 15.8 ⁇ .
  • SEM images showed spherical agglomerates of the yellow powder held together internally by the organic component lactose / mannitol.
  • Inventive electrode material was processed with a binder (iv.1): copolymer of vinylidene fluoride and hexafluoropropene, as a powder, commercially available as Kynar Flex® 2801 from Arkema, Inc., as follows.
  • a binder iv.1: copolymer of vinylidene fluoride and hexafluoropropene, as a powder, commercially available as Kynar Flex® 2801 from Arkema, Inc., as follows.
  • 8 g of electrode material according to the invention from step EM.1 and 1 g (iv.1) with the addition of 1 g of N-methylpyrrolidone (NMP) and 1 g of carbon black were mixed to form a paste. It is coated a 30 ⁇ thick aluminum foil with the paste described above (active material loading 4 mg / cm 2 ). After drying, but without compression, at 105 ° C, circular parts of the thus coated aluminum foil (diameter 20 mm
  • the electrolyte As the electrolyte, a 1 mol / l solution of LiPF6 in ethylene carbonate / dimethyl carbonate (1: 1 based on mass fractions) was used.
  • the anode of the test cells consisted of a lithium foil, which is in contact with the cathode foil via a separator made of glass fiber paper.
  • the invention gives electrochemical cells EZ.1.
  • step (a.8) the following starting materials were used:
  • Step (b.8) Drying The solution from step (a.1) was diluted at max. Concentrated 85 ° C and 10 mbar for about 5 h. This gave a sticky, viscous, yellow mass. This was dried at 95 ° C for about 12 h. A yellow powder was obtained step (c.8) - calcination
  • 60 g of the powder obtained as described above were thermally treated in a 2 liter quartz rotary kiln under an atmosphere of IS.
  • the 2 liter quartz spin ball rotated at a speed of 10 rpm. First, it was heated to 700 ° C within 60 minutes. Then calcined for 60 minutes at 700 ° C. Thereafter, the mixture was allowed to cool to room temperature.
  • FIG. 1 shows a scanning electron micrograph of the resulting electrode material EM.8. One recognizes a finely divided homogeneous material.
  • the mixture was stirred at RT for a period of four hours. A yellow, non-homogeneous suspension solution was obtained. After the experiment, particles of a dark substance were still present in the reaction mixture. After the additional addition of ethanol, the experimental picture has not changed. The reaction mixture is not homogeneous as in the preparation of EM.8.
  • step (a.1) The solution from step (a.1) was diluted at max. Concentrated 80 ° C and 25 mbar for about 5 h. This gave a sticky, yellow mass. This was dried in a convection oven at 95 ° C over a period of 24 hours. A yellow powder was obtained. Step (c.9) - Calcination
  • 60 g of the material as described above were thermally treated in a 2 liter quartz rotary kiln under N 2 atmosphere.
  • the 2-liter quartz spin ball rotated at a speed of speed of 10 revolutions / min. First, it was heated to 700 ° C within 60 minutes. Then calcined for 60 minutes at 700 ° C. Then allowed to cool to room temperature.
  • V-EM.9 Part of the calcined material was crushed in a mortar and sieved (mesh 40 ⁇ ). The electrode material V-EM.9 was obtained, which looked black and was obtained in powder form. V-EM.9 can not be further processed into a homogeneous paste with low viscosity.
  • FIG. 2 shows a scanning electron micrograph of the comparative electrode material V-EM.9. One recognizes uneven, cohesive material of coarse structure.

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Abstract

The present invention relates to a method for producing electrode materials, characterized in that the method comprises the following steps: (a) the following are mixed with each other: (A) at least one phosphorus compound, (B) at least one lithium compound, (C) at least one carbon source, (D1) at least one water-soluble iron compound, in which Fe is present in the oxidation state +2 or +3, (D2) at least one iron source, which is different from (D1) and water-insoluble and in which Fe is present in the oxidation state zero, +2, or +3, and (b) the obtained mixture is thermally treated.

Description

Verfahren zur Herstellung von Elektrodenmaterialien  Process for the production of electrode materials
Beschreibung Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von Elektrodenmaterialien, das die folgenden Schritte beinhaltet: The present invention relates to a process for the production of electrode materials, which comprises the following steps:
(a) man vermischt in Gegenwart von Wasser oder in Gegenwart von Wasser und organischem Lösungsmittel miteinander:  (a) mixing together in the presence of water or in the presence of water and organic solvent:
(A) mindestens eine Phosphorverbindung,  (A) at least one phosphorus compound,
(B) mindestens eine Lithiumverbindung,  (B) at least one lithium compound,
(C) mindestens eine Kohlenstoffquelle,  (C) at least one carbon source,
(D1 ) mindestens eine wasserlösliche Eisenverbindung, in der Fe in der Oxidationsstufe +2 oder +3 vorliegt,  (D1) at least one water-soluble iron compound in which Fe is in the oxidation state +2 or +3,
(D2) mindestens eine Eisenquelle, die von (D1 ) verschieden und wasserunlöslich ist und in der Fe in der Oxidationsstufe null, +2 oder +3 vorliegt,  (D2) at least one iron source which is different from (D1) and insoluble in water and in which Fe is in the oxidation state zero, +2 or +3,
(b) man behandelt die erhaltene Mischung thermisch.  (b) treating the resulting mixture thermally.
Weiterhin betrifft die vorliegende Erfindung Elektrodenmaterialien und deren Verwendung sowie Lithiumionenbatterien, die Elektroden aus diesem Material enthalten. Bevorzugte Ausführungs- formen sind den Ansprüchen und der Beschreibung der Erfindung zu entnehmen. Kombinationen von bevorzugten Ausführungsformen fallen in den Rahmen der vorliegenden Erfindung. Furthermore, the present invention relates to electrode materials and their use and lithium ion batteries containing electrodes of this material. Preferred embodiments are to be taken from the claims and the description of the invention. Combinations of preferred embodiments are within the scope of the present invention.
Auf der Suche nach vorteilhaften Elektrodenmaterialien für Batterien, die als leitfähige Spezies Lithium-Ionen nutzen, wurden bisher zahlreiche Materialien vorgeschlagen, beispielsweise Li- thium-haltige Spinelle, Mischoxide mit Schichtstruktur wie beispielsweise lithiierte Nickel- Mangan-Kobalt-Oxide und Lithium-Eisen-Phosphate. In the search for advantageous electrode materials for batteries which use lithium ions as conductive species, numerous materials have hitherto been proposed, for example lithium-containing spinels, layered mixed oxides such as, for example, lithiated nickel-manganese-cobalt oxides and lithium-iron oxides. phosphates.
Lithium-Eisen-Phosphate sind deshalb von besonderem Interesse, weil sie keine toxischen Schwermetalle enthalten und in vielen Fällen sehr robust gegen Oxidation und Wasser sind. Nachteilig bei Lithium-Eisen-Phosphaten kann die vergleichsweise geringe Energiedichte sein. Lithium iron phosphates are of particular interest because they contain no toxic heavy metals and in many cases are very robust against oxidation and water. A disadvantage of lithium iron phosphates may be the comparatively low energy density.
Ein Verfahren zur Herstellung von Lithium-Eisen-Phosphaten in Gegenwart von organischen Lösungsmitteln zur Verwendung in Lithiumionenbatterien ist in WO 09/015565 offenbart. Ein Problem besteht darin, dass Batterien auf der Basis von Lithiumeisenphosphaten in einigen Anwendungsformen, in denen eine hohe Spitzenleistung gefordert wird, beispielsweise für Ak- kubohrschrauber, mit denen man in Beton bohren und schrauben möchte, unbefriedigend sind. Weitere Beispiele sind Anlasser für Kraftfahrzeuge und Krafträder. Als problematisch wird dabei gesehen, dass die gewünschte schnelle Entladung bei Lithium-Ionen-Batterien auf Basis von Lithiumeisenphosphaten nicht geleistet wird. A process for producing lithium iron phosphates in the presence of organic solvents for use in lithium ion batteries is disclosed in WO 09/015565. One problem is that batteries based on lithium iron phosphates are unsatisfactory in some applications in which high peak power is required, for example for cordless screwdrivers with which you want to drill and screw in concrete. Other examples are starters for motor vehicles and motorcycles. It is seen as problematic that the desired rapid discharge is not achieved with lithium-ion batteries based on lithium iron phosphates.
Es bestand also die Aufgabe, elektrochemische Zellen bereit zu stellen, die toxikologisch möglichst wenig bedenkliche Elektrodenmaterialien enthalten und die eine schnelle Entladung, also eine hohe Spitzenleistung aufweisen. Weiterhin bestand die Aufgabe, ein Verfahren bereit zu stellen, nach dem man Elektrodenmaterialien herstellen kann, und die eine schnelle Entladung, also eine hohe Spitzenleistung, der korrespondierenden Batterien ermöglichen. Dementsprechend wurde das eingangs definierte Verfahren gefunden, im Folgenden auch als erfindungsgemäßes Verfahren bezeichnet. It was therefore the task to provide electrochemical cells that contain toxicologically as little questionable electrode materials and the rapid discharge, ie have a high peak performance. Furthermore, the object was to provide a method by which one can produce electrode materials, and allow a fast discharge, so a high peak power, the corresponding batteries. Accordingly, the method defined above was found, hereinafter also referred to as inventive method.
Zur Durchführung des erfindungsgemäßen Verfahrens vermischt man in Stufe (a) mehrere der Ausgangsmaterialien, vorzugsweise alle beteiligten Ausgangsmaterialien, in mehreren oder vorzugsweise in einem Schritt. Als Gefäße für das Vermischen sind beispielsweise Rührkessel und gerührte Kolben geeignet. For carrying out the process according to the invention, in stage (a) several of the starting materials, preferably all the starting materials involved, are mixed in several or preferably in one step. As vessels for mixing, for example, stirred tank and stirred flasks are suitable.
Im Folgenden werden die Ausgangsmaterialien weiter charakterisiert. Als Ausgangsmaterial (A) wählt man mindestens eine Phosphorverbindung, im Folgenden auch Phosphorverbindung (A) genannt, gewählt aus Phosphorwasserstoffen und Verbindungen, in denen Phosphor in der Oxidationsstufe +1 oder +3 oder +5 vorliegt, beispielsweise Phosphanen mit mindestens einer Alkylgruppe oder mindestens einer Alkoxygruppe pro Molekül, Phosphor- halogeniden, Phosphonsäure, hypophosphoriger Säure und Phosphorsäure. Bevorzugte Phos- phane sind solche der allgemeinen Formel (I) wobei die Variablen wie folgt gewählt sind: In the following, the starting materials are further characterized. The starting material (A) is selected from at least one phosphorus compound, hereinafter also called phosphorus compound (A), selected from phosphine and compounds in which phosphorus in the oxidation state +1 or +3 or +5, for example phosphines having at least one alkyl group or at least an alkoxy group per molecule, phosphorus halides, phosphonic acid, hypophosphorous acid and phosphoric acid. Preferred phosphanes are those of the general formula (I) where the variables are chosen as follows:
R1 kann verschieden sein oder gleich und ist gewählt aus Phenyl und vorzugsweise C1-C10- Alkyl, cyclisch oder linear, beispielsweise Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso- Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, Cyclopentyl, iso-Amyl, iso-Pentyl, n-Hexyl, iso- Hexyl, Cyclohexyl, und 1 ,-3-Dimethylbutyl, bevorzugt n-Ci-C6-Alkyl, besonders bevorzugt Methyl, Ethyl, n-Propyl, iso-Propyl und ganz besonders bevorzugt Methyl oder Ethyl.R 1 may be different or the same and is selected from phenyl and preferably C 1 -C 10 -alkyl, cyclic or linear, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, cyclopentyl, iso-amyl, iso-pentyl, n-hexyl, iso-hexyl, cyclohexyl, and 1, 3-dimethylbutyl, preferably n-Ci-C6-alkyl, particularly preferably methyl, Ethyl, n-propyl, isopropyl, and most preferably methyl or ethyl.
Wenn ein Stoff mehrere Alkoxygruppen pro Mol aufweist, so kann R1 verschieden sein oder vorzugsweise gleich und gewählt aus den vorstehend genannten Ci-C6-Alkylresten. If a substance has several alkoxy groups per mole, then R 1 may be different or preferably the same and selected from the abovementioned C 1 -C 6 -alkyl radicals.
X1 kann verschieden sein oder gleich und wird gewählt aus Halogen, Hydroxylgruppen, Phe- noxygruppen und Alkoxygruppen, bevorzugt der Formel OR1, insbesondere Methoxy undX 1 may be different or the same and is selected from halogen, hydroxyl groups, phenoxy groups and alkoxy groups, preferably of the formula OR 1 , in particular methoxy and
Ethoxy, und wobei Halogen bevorzugt Brom und besonders bevorzugt Chlor ist, r, s sind gewählt aus ganzen Zahlen im Bereich von null bis drei, Ethoxy, and where halogen is preferably bromine and more preferably chlorine, r, s are selected from integers in the range of zero to three,
t ist gewählt aus ganzen Zahlen im Bereich von null bis zwei, wobei die Summe r + s + t = 3, und wobei mindestens eine der Ungleichungen r * 0 t is selected from integers ranging from zero to two, where the sum is r + s + t = 3, and where at least one of the inequalities r * 0
s * 0 erfüllt ist. s * 0 is satisfied.
In einer Ausführungsform der vorliegenden Erfindung wählt man Phosphorverbindung (A) aus Verbindungen der allgemeinen Formel P(OR1)3, wobei R1 verschieden oder vorzugsweise gleich sein kann und gewählt aus Phenyl und Ci-Cio-Alkyl, besonders bevorzugt sind P(OCH3)3 und P(OC2H5)3. In one embodiment of the present invention, phosphorus compound (A) is selected from compounds of general formula P (OR 1 ) 3, wherein R 1 may be different or preferably the same and selected from phenyl and C 1 -C 10 -alkyl, more preferably P (OCH 3 ) 3 and P (OC 2 H 5 ) 3 .
In einer Ausführungsform der vorliegenden Erfindung wählt man Phosphorverbindung (A) aus Verbindungen der allgemeinen Formel wobei R1 verschieden oder vorzugsweise gleich sein kann und gewählt aus Phenyl und Ci-Cio-Alkyl, besonders bevorzugt sind In one embodiment of the present invention, phosphorus compound (A) is selected from compounds of the general formula wherein R 1 may be different or preferably the same and selected from phenyl and C 1 -C 10 -alkyl, are particularly preferred
0=P(OCH3)3 und 0=P(OC2H5)3. 0 = P (OCH 3 ) 3 and 0 = P (OC 2 H 5 ) 3 .
In einer Ausführungsform der vorliegenden Erfindung wählt man Phosphorverbindung (A) aus Verbindungen der allgemeinen Formel wobei R1 verschieden oder vorzugsweise gleich sein kann und gewählt aus Phenyl und Ci-Cio-Alkyl, besonders bevorzugt sind In one embodiment of the present invention, phosphorus compound (A) is selected from compounds of the general formula wherein R 1 may be different or preferably the same and selected from phenyl and C 1 -C 10 -alkyl, are particularly preferred
0=P(C6H5)3, 0=P(CH3)3 und 0=P(C2H5)3. 0 = P (C 6 H 5 ) 3 , 0 = P (CH 3 ) 3 and 0 = P (C 2 H 5 ) 3 .
Als Phosphonsäure, hypophosphorige Säure und Phosphorsäure kann man jeweils die freie Säure oder korrespondierende Salze wählen, insbesondere Lithium- und Ammoniumsalze. Als Phosphorsäure und Phosphonsäure kann man jeweils die einkernigen Säuren H3P03 bzw. H3P04 wählen, weiterhin aber auch zwei-, drei- oder mehrkernige Säuren, beispielsweise Η4Ρ2θ7 oder Polyphosphorsäure. In einer anderen Variante wählt man eine gemischt kondensierte Verbindung, beispielsweise erhältlich durch Kondensation von Phosphorsäure mit Phosphoriger Säure. As phosphonic acid, hypophosphorous acid and phosphoric acid can be selected in each case the free acid or corresponding salts, in particular lithium and ammonium salts. As phosphoric acid and phosphonic acid can be selected in each case the mononuclear acids H 3 P0 3 or H 3 P0 4 , but also two-, three- or polynuclear acids, for example Ρ 4 Ρ2θ7 or polyphosphoric acid. In another variant, a mixed condensed compound is selected, for example obtainable by condensation of phosphoric acid with phosphorous acid.
In einer Ausführungsform der vorliegenden Erfindung wählt man als Ausgangsmaterial (A) zwei oder mehr Phosphorverbindungen (A). In einer anderen Ausführungsform der vorliegenden Erfindung wählt man genau eine Phosphorverbindung (A). Als Ausgangsmaterial (B) wählt man mindestens eine Lithiumverbindung, auch Lithiumverbindung (B) genannt, vorzugsweise mindestens eine anorganische Lithiumverbindung. Beispiele für geeignete anorganische Lithiumverbindungen sind Lithiumhalogenide, beispielsweise Lithiumchlorid, weiterhin Lithiumsulfat, Lithiumacetat, LiOH, Li2C03, L12O und LiN03; bevorzugt sind L12SC , LiOH, Li2C03, L12O und LiN03. Dabei kann Lithiumverbindung Kristallwasser enthalten, beispielsweise LiOH ■ H2O. In one embodiment of the present invention, as the starting material (A), two or more phosphorus compounds (A) are selected. In another embodiment of the present invention, exactly one phosphorus compound (A) is chosen. The starting material (B) is selected from at least one lithium compound, also called lithium compound (B), preferably at least one inorganic lithium compound. Examples of suitable inorganic lithium compounds are lithium halides, for example lithium chloride, furthermore lithium sulfate, lithium acetate, LiOH, Li 2 CO 3 , L 12 O and LiNO 3 ; preferred are L12SC, LiOH, Li2C0 3 , L12O and LiN0 3 . In this case, lithium compound can contain water of crystallization, for example LiOH ■ H2O.
In einer speziellen Ausführungsform der vorliegenden Erfindung wählt man als Phosphorverbindung (A) und Lithiumverbindung (B) jeweils L1H2PO2, Lithiumphosphat, Lithiumorthophosphat, Lithiummetaphosphat, Lithiumphosphonat, Lithiumphosphit, Lithiumhydrogenphoshat oder Li- thiumdihydrogenphosphat, d.h., Lithiumphosphat, Lithiumphosphonat, Lithiumphosphit oder Lithium(di)hydrogenphosphat können jeweils gleichzeitig als Phosphorverbindung (A) und als Lithiumverbindung (B) dienen. In a specific embodiment of the present invention, the phosphorus compound (A) and lithium compound (B) are each selected as L1H 2 PO 2, lithium phosphate, lithium orthophosphate, Lithium metaphosphate, lithium phosphonate, lithium phosphite, lithium hydrogen phosphate or lithium dihydrogen phosphate, ie, lithium phosphate, lithium phosphonate, lithium phosphite or lithium (di) hydrogen phosphate may each serve simultaneously as phosphorus compound (A) and as lithium compound (B).
Als Ausgangsmaterial (C) wählt man mindestens eine Kohlenstoffquelle, kurz auch Kohlenstoffquelle (C) genannt, die eine separate Kohlenstoffquelle oder gleich mindestens einer Phosphorverbindung (A) oder Lithiumverbindung (B) sein kann. Unter einer separaten Kohlenstoffquelle (C) soll im Rahmen dieser Erfindung verstanden werden, dass ein weiteres Ausgangsmaterial eingesetzt wird, das gewählt wird aus elementarem Kohlenstoff in einer Modifikation, die den elektrischen Strom leitet, oder eine Verbindung, die im Rahmen der thermischen Behandlung in Schritt (b) zu Kohlenstoff zersetzt wird und die von Phosphorverbindung (A) und Lithiumverbindung (B) verschieden ist. The starting material (C) is selected from at least one carbon source, also called carbon source (C), which may be a separate carbon source or at least one phosphorus compound (A) or lithium compound (B). For the purposes of the present invention, a separate carbon source (C) is to be understood as meaning that a further starting material is used which is selected from elemental carbon in a modification which conducts the electric current or a compound which is used in the thermal treatment in step (b) is decomposed into carbon and different from phosphorus compound (A) and lithium compound (B).
Als Kohlenstoffquelle (C) ist beispielsweise Kohlenstoff in einer Modifikation, die den elektrischen Strom leitet, geeignet, also beispielsweise Ruß, Graphit, Graphen, Kohlenstoff- Nanoröhren oder Aktivkohle. Beispiele für Graphit sind nicht nur mineralischer und synthetischer Graphit, sondern auch expandierte Graphite und interkalierter Graphit. As the carbon source (C), for example, carbon in a modification that conducts the electric current is suitable, for example, carbon black, graphite, graphene, carbon nanotubes or activated carbon. Examples of graphite are not only mineral and synthetic graphite, but also expanded graphite and intercalated graphite.
Ruß kann beispielsweise gewählt werden aus Lampenruß, Ofenruß, Flammruß, Thermalruß, Acetylenruß, Industrieruß und Furnace Ruß. Ruß kann Verunreinigungen enthalten, beispiels- weise Kohlenwasserstoffe, insbesondere aromatische Kohlenwasserstoffe, oder Sauerstoffhaltige Verbindungen bzw. Sauerstoff-haltige Gruppen wie beispielsweise OH-Gruppen. Weiterhin sind Schwefel- oder Eisen-haltige Verunreinigungen in Ruß möglich. In einer weiteren Variante setzt man modifizierte Ruße oder modifizierte Graphite ein, beispielsweise solche Ruße oder Graphite, die Hydroxylgruppen, Epoxygruppen, Ketogruppen oder Carboxylgruppen aufweisen. Carbon black may, for example, be selected from lampblack, furnace black, flame black, thermal black, acetylene black, carbon black and furnace carbon black. Carbon black may contain impurities, for example hydrocarbons, in particular aromatic hydrocarbons, or oxygen-containing compounds or oxygen-containing groups, for example OH groups. Furthermore, sulfur or iron-containing impurities in carbon black are possible. In a further variant, modified carbon blacks or modified graphites are used, for example those carbon blacks or graphites which have hydroxyl groups, epoxy groups, keto groups or carboxyl groups.
Als Kohlenstoffquelle (C) sind weiterhin Verbindungen von Kohlenstoff geeignet, die bei der thermischen Behandlung in Schritt (c) zu Kohlenstoff zersetzt werden. Beispielsweise sind synthetische und natürliche Polymere, unmodifiziert oder modifiziert, geeignet. Beispiele für synthe- tische Polymere sind Polyolefine, beispielsweise Polyethylen und Polypropylen, weiterhin Poly- acrylnitril, Polybutadien, Polystyrol, und Copolymeren von mindestens zwei Comonomeren, gewählt aus Ethylen, Propylen, Styrol, (Meth)acrylnitril und 1 ,3-Butadien. Weiterhin sind Poly- isopren und Polyacrylate geeignet. Besonders bevorzugt ist Polyacrylnitril. Unter Polyacrylnitril werden im Rahmen der vorliegenden Erfindung nicht nur Polyacrylnitril- Homopolymere verstanden, sondern auch Copolymere von Acrylnitril mit 1 ,3-Butadien oder Styrol. Bevorzugt sind Polyacrylnitril-Homopolymere. Im Rahmen der vorliegenden Erfindung wird unter Polyethylen nicht nur Homo-Polyethylen verstanden, sondern auch Copolymere des Ethylens, die mindestens 50 mol-% Ethylen einpolyme- risiert enthalten und bis zu 50 mol-% von mindestens einem weiteren Comonomer, beispiels- weise α-Olefine wie Propylen, Butylen (1 -Buten), 1 -Hexen, 1 -Octen, 1 -Decen, 1 -Dodecen, 1 - Penten, weiterhin Isobuten, Vinylaromaten wie beispielsweise Styrol, weiterhin As the carbon source (C), further compounds of carbon are suitable, which are decomposed to carbon during the thermal treatment in step (c). For example, synthetic and natural polymers, unmodified or modified, are suitable. Examples of synthetic polymers are polyolefins, for example polyethylene and polypropylene, furthermore polyacrylonitrile, polybutadiene, polystyrene, and copolymers of at least two comonomers selected from ethylene, propylene, styrene, (meth) acrylonitrile and 1,3-butadiene. Furthermore, polyisoprene and polyacrylates are suitable. Particularly preferred is polyacrylonitrile. In the context of the present invention, polyacrylonitrile is understood to mean not only polyacrylonitrile homopolymers, but also copolymers of acrylonitrile with 1,3-butadiene or styrene. Preference is given to polyacrylonitrile homopolymers. In the context of the present invention, polyethylene is understood to mean not only homo-polyethylene, but also copolymers of ethylene which contain at least 50 mol% of ethylene in copolymerized form and up to 50 mol% of at least one further comonomer, for example Olefins such as propylene, butylene (1-butene), 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-pentene, also isobutene, vinyl aromatics such as styrene, further
(Meth)acrylsäure, Vinylacetat, Vinylpropionat, Ci-Cio-Alkylester der (Meth)acrylsäure, insbesondere Methylacrylat, Methylmethacrylat, Ethylacrylat, Ethylmethacrylat, n-Butylacrylat, 2- Ethylhexylacrylat, n-Butylmethacrylat, 2-Ethylhexylmethacrylat, weiterhin Maleinsäure, Malein- säureanhydrid und Itaconsäureanhydrid. Bei Polyethylen kann es sich um HDPE oder um LDPE handeln. (Meth) acrylic acid, vinyl acetate, vinyl propionate, C 1 -C 10 -alkyl esters of (meth) acrylic acid, in particular methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, 2-ethylhexyl acrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, furthermore maleic acid, maleic acid acid anhydride and itaconic anhydride. Polyethylene may be HDPE or LDPE.
Im Rahmen der vorliegenden Erfindung wird unter Polypropylen nicht nur Homo-Polypropylen verstanden, sondern auch Copolymere des Propylens, die mindestens 50 mol-% Propylen ein- polymerisiert enthalten und bis zu 50 mol-% von mindestens einem weiteren Comonomer, beispielsweise Ethylen und α-Olefine wie Butylen, 1 -Hexen, 1 -Octen, 1 -Decen, 1 -Dodecen und 1 - Penten. Bei Polypropylen handelt es sich vorzugsweise um isotaktisches oder um im Wesentlichen isotaktisches Polypropylen. Im Rahmen der vorliegenden Erfindung werden unter Polystyrol nicht nur Homopolymere des Styrols verstanden, sondern auch Copolymere mit Acrylnitril, 1 ,3-Butadien, (Meth)acrylsäure, Ci-Cio-Alkylester der (Meth)acrylsäure, Divinylbenzol, insbesondere 1 ,3-Divinylbenzol, 1 ,2- Diphenylethylen und a-Methylstyrol. Ein weiteres geeignetes synthetisches Polymer ist Polyvinylalkohol. In the context of the present invention, polypropylene is understood to mean not only homo-polypropylene but also copolymers of propylene which contain at least 50 mol% of propylene polymerized and up to 50 mol% of at least one further comonomer, for example ethylene and α-propylene. Olefins such as butylene, 1-hexene, 1-octene, 1-decene, 1-dodecene and 1-pentene. Polypropylene is preferably isotactic or substantially isotactic polypropylene. In the context of the present invention, polystyrene is understood to mean not only homopolymers of styrene, but also copolymers with acrylonitrile, 1,3-butadiene, (meth) acrylic acid, C 1 -C 10 -alkyl esters of (meth) acrylic acid, divinylbenzene, in particular 1, 3. Divinylbenzene, 1, 2-diphenylethylene and a-methylstyrene. Another suitable synthetic polymer is polyvinyl alcohol.
Als Kohlenstoffquelle (C) geeignete natürliche Polymere sind beispielsweise Stärke, Zellulose, Alginate, (z. B. Agar-Agar, weiterhin Pektine, Gummi arabicum, Oligo-und Polysaccharide, Guarkernmehl und Johannisbrotkernmehl sowie Amylose und Amylopektin geeignet. Suitable natural polymers as carbon source (C) are, for example, starch, cellulose, alginates (eg agar agar, furthermore pectins, gum arabic, oligo and polysaccharides, guar gum and locust bean gum as well as amylose and amylopectin.
Geeignet sind auch modifizierte natürliche Polymere. Darunter seien durch polymeranaloge Umsetzung modifizierte natürliche Polymere verstanden. Geeignete polymeranaloge Umsetzungen sind insbesondere die Veresterung und die Veretherung. Bevorzugte Beispiele für modifizierte natürliche Polymere sind mit Methanol veretherte Stärke, acetylierte Stärke und Ace- tylcellulose, weiterhin phosphatierte und sulfatierte Stärke. Also suitable are modified natural polymers. These are understood to mean by polymer-analogous reaction modified natural polymers. Suitable polymer-analogous reactions are, in particular, the esterification and the etherification. Preferred examples of modified natural polymers are methanol-etherified starch, acetylated starch and acetyl cellulose, furthermore phosphated and sulfated starch.
Weiterhin sind als Kohlenstoffquelle (C) Carbide geeignet, bevorzugt kovalente Carbide, beispielsweise Eisencarbid FesC. Weiterhin sind schwerflüchtige niedermolekulare organische Verbindungen als Kohlenstoffquelle (C) geeignet. Geeignet sind insbesondere solche Verbindungen, die bei Temperaturen im Bereich von 350 bis 1200°C nicht verdampfen, sondern sich zersetzen, beispielsweise als Fest- stoff oder in der Schmelze. Beispiele sind Dicarbonsäuren, beispielsweise Phthalsäure, Phthal- säureanydrid, Isophthalsäure, Terephthalsäure, Weinsäure, Zitronensäure, Brenztraubensäure, weiterhin Zucker, beispielsweise Monosaccharide mit 3 bis 7 Kohlenstoffatomen pro Molekül (Triosen, Tetrosen, Pentosen, Hexosen, Heptosen) und Kondensate von Monosacchariden wie beispielsweise Di-, Tri-, und Oligosaccharide, insbesondere Laktose, Glucose und Fructose, außerdem Zuckeralkohole und Zuckersäuren, beispielsweise Aldonsäuren, Ketoaldonsäuren, Uronsäuren und Aldarsäuren, insbesondere Galactonsäure. Furthermore, carbides are suitable as the carbon source (C), preferably covalent carbides, for example iron carbide FesC. Furthermore, low volatility low molecular weight organic compounds are suitable as carbon source (C). Particularly suitable compounds are those which do not evaporate at temperatures in the range from 350 to 1200 ° C., but decompose, for example as solids. or in the melt. Examples are dicarboxylic acids, for example phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, tartaric acid, citric acid, pyruvic acid, furthermore sugars, for example monosaccharides having 3 to 7 carbon atoms per molecule (trioses, tetroses, pentoses, hexoses, heptoses) and condensates of monosaccharides such as, for example Di-, tri- and oligosaccharides, in particular lactose, glucose and fructose, as well as sugar alcohols and sugar acids, for example aldonic acids, ketoaldonic acids, uronic acids and aldaric acids, in particular galactonic acid.
Weitere Beispiele für niedermolekulare organische Verbindungen als Kohlenstoffquelle (C) sind Harnstoff sowie seine schwerer flüchtigen Kondensate Biuret, Melamin, Melam (N2-(4,6- diamino-1 ,3,5-triazin-2-yl)-1 ,3,5-triazin-2,4,6-triamin) und Meiern (1 ,3,4,6,7,9,9b- Heptaazaphenalen-2,5,8-triamin). Further examples of low molecular weight organic compounds as carbon source (C) are urea and its less volatile condensates biuret, melamine, melam (N2- (4,6-diamino-1, 3,5-triazin-2-yl) -1, 3, 5-triazine-2,4,6-triamine) and Meiern (1, 3,4,6,7,9,9b-heptaazaphenalene-2,5,8-triamine).
Weitere Beispiele für Kohlenstoffquellen (C) sind Salze, bevorzugt Eisen-, Ammoniumsalze und Alkalimetallsalze, besonders bevorzugt Eisen-, Natrium-, Kalium-, Ammonium- oder Lithiumsalze, von organischen Säuren, beispielsweise Alkanoate, insbesondere Acetate, Propionate, Butyrate, weiterhin Lactate, Citrate, Tartrate und Benzoate. Besonders bevorzugte Beispiele sind Ammoniumacetat, Kaliumammoniumtartrat, Kaliumhydrogentartrat, Kaliumnatriumtartrat, Natriumtartrat (Dinatriumtartrat), Natriumhydrogentartrat, Lithiumhydrogentatrat, Lithiumammo- niumtatrat, Lithiumtartrat, Lithiumeitrat, Kaliumeitrat, Natriumeitrat, Eisenacetat, Lithiumacetat, Natriumacetat, Kaliumacetat, Lithiumlactat, Ammoniumlactat, Natriumlactat und Kaliumlactat. Further examples of carbon sources (C) are salts, preferably iron, ammonium salts and alkali metal salts, more preferably iron, sodium, potassium, ammonium or lithium salts, of organic acids, for example alkanoates, in particular acetates, propionates, butyrates, furthermore lactates , Citrates, tartrates and benzoates. Particularly preferred examples are ammonium acetate, potassium ammonium tartrate, potassium hydrogen tartrate, potassium sodium tartrate, sodium tartrate, sodium hydrogen tartrate, lithium hydrogentate, lithium ammonium tartrate, lithium tartrate, lithium citrate, potassium citrate, sodium citrate, iron acetate, lithium acetate, sodium acetate, potassium acetate, lithium lactate, ammonium lactate, sodium lactate and potassium lactate.
In einer speziellen Ausführungsform der vorliegenden Erfindung wählt man als Kohlenstoffquelle (C) und Phosphorverbindung (A) eine organische Phosphorverbindung, genannt seien bei- spielsweise Phosphorsäuretrimethylester, Phosphorsäuretriethylester, Triphenylphosphan und Triphenylphosphinoxid (CeHs^PO. In a specific embodiment of the present invention, the carbon source (C) and phosphorus compound (A) used are an organic phosphorus compound, for example trimethyl phosphate, triethyl phosphite, triphenyl phosphine and triphenyl phosphine oxide (CeH.sub.3 PO).
In einer speziellen Ausführungsform der vorliegenden Erfindung wählt man als Kohlenstoffquelle (C) und Lithiumverbindung (B) jeweils Lithiumacetat, Lithiumlactat oder Lithiumhydrogentart- rat, d.h. Lithiumverbindung (B) Lithiumacetat, Lithiumlactat bzw. Lithiumhydrogentartrat können jeweils gleichzeitig als Kohlenstoffquelle (C) dienen. In a specific embodiment of the present invention, the respective carbon source (C) and lithium compound (B) are selected from lithium acetate, lithium lactate or lithium hydrogen tartrate, i. Lithium compound (B) Lithium acetate, lithium lactate or lithium hydrogen tartrate can each serve simultaneously as carbon source (C).
In einer Ausführungsform der vorliegenden Erfindung wählt man zwei oder mehr verschiedene Kohlenstoffquellen, beispielsweise zwei verschiedene Kohlenstoffquellen oder drei verschiede- ne Kohlenstoffquellen. In einer anderen Ausführungsform der vorliegenden Erfindung wählt man genau eine Kohlenstoffquelle (C). In one embodiment of the present invention, one chooses two or more different carbon sources, for example two different carbon sources or three different carbon sources. In another embodiment of the present invention, one chooses exactly one carbon source (C).
Als Ausgangsmaterial (D) wählt man mindestens zwei Eisenverbindungen oder Eisen und mindestens eine Eisenverbindung (D1 ). Dabei wählt man As starting material (D), at least two iron compounds or iron and at least one iron compound (D1) are selected. You choose
(D1 ) mindestens eine wasserlösliche Eisenverbindung, in der Fe in der Oxidationsstufe +2 oder(D1) at least one water-soluble iron compound in which Fe in the oxidation state +2 or
+3 vorliegt, kurz auch als„Eisenverbindung (D1 )" oder„Komponente (D1 )" bezeichnet, und (D2) mindestens eine Eisenquelle, die von (D1 ) verschieden und wasserunlöslich ist und in der Fe in der Oxidationsstufe null, +2 oder +3 vorliegt. +3, also referred to as "iron compound (D1)" or "component (D1)" for short, and (D2) at least one iron source which is different from (D1) and insoluble in water and in which Fe is in the oxidation state zero, +2 or +3.
Beispielsweise kann man als Eisenquelle (D2) Eisen oder vorzugsweise mindestens eine was- serunlösliche Eisenverbindung wählen, in der Fe in der Oxidationsstufe null, +2 oder +3 vorliegt, kurz auch als„Eisenverbindung (D2)" oder„Komponente (D2)" bezeichnet. For example, iron source (D2) may be selected from iron or preferably at least one water-insoluble iron compound in which Fe is in the oxidation state zero, +2 or +3, also referred to as "iron compound (D2)" or "component (D2)". designated.
Dabei bedeutet„in der Oxidationsstufe +2 oder +3" die Oxidationsstufe, in der Fe in der betreffenden Eisenverbindung (D1 ) bzw. Eisenverbindung (D2) zu Beginn des Vermischens nach Schritt (a) vorliegt. In this case, "in the oxidation state +2 or +3" means the oxidation state in which Fe is present in the relevant iron compound (D1) or iron compound (D2) at the beginning of the mixing after step (a).
Unter„wasserlöslich" wird im Zusammenhang mit Eisenverbindung (D1 ) verstanden, dass die Löslichkeit in voll entsalztem Wasser bei einem pH-Wert von 7 und 20°C mindestens 0,1 g Fe- lonen/l beträgt, bevorzugt im Bereich von 1 bis 500 g/l. "Water-soluble" in connection with iron compound (D1) is understood to mean that the solubility in demineralized water at a pH of 7 and 20 ° C. is at least 0.1 g Fe ions / l, preferably in the range from 1 to 500 g / l.
Unter„wasserunlöslich" wird im Zusammenhang mit Eisenverbindung (D2) verstanden, dass die Löslichkeit in voll entsalztem Wasser bei einem pH-Wert von 7 und 20°C weniger als 0,1 g Fe- lonen/l beträgt, beispielsweise 10"10 bis 0,01 g/l. Bei Eisenverbindung (D1 ) und bei Eisenverbindung (D2) handelt es sich vorzugsweise um anorganische Eisenverbindungen. By "water-insoluble" is meant in connection with iron compound (D2) that the solubility in demineralized water at a pH of 7 and 20 ° C is less than 0.1 g Fe ions / l, for example 10 "10 bis 0.01 g / l. Iron compound (D1) and iron compound (D2) are preferably inorganic iron compounds.
Dabei kann man Eisenverbindung (D1 ) aus wasserfreien und wasserhaltigen Eisenverbindungen wählen, beispielsweise den Hydraten. Dabei sollen unter Hydraten nicht nur Monohydrate, sondern auch andere Hydrate verstanden werden, beispielsweise im Falle des Eisen(ll)oxalat auch das Dihydrat, im Falle des Eisen(ll)chlorids auch das Tetrahydrat und im Falle des Ei- sen(lll)nitrats auch das Nonahydrat. In this case, one can choose iron compound (D1) from anhydrous and hydrous iron compounds, such as the hydrates. Hydrates are to be understood as meaning not only monohydrates but also other hydrates, for example, in the case of iron (II) oxalate, also the dihydrate, in the case of iron (II) chloride also the tetrahydrate and in the case of iron (III) nitrate also the nonahydrate.
In einer Ausführungsform der vorliegenden Erfindung wählt man wasserlösliche Eisenverbin- dung (D1 ) aus Ammoniumeisen(ll)sulfat, Ammoniumeisen(lll)sulfat,, Ammoniumeisen(ll)citrat, Ammoniumeisen(lll)citrat, Eisen(ll)bromid, Eisen(lll)bromid, Eisen(ll)fluorid, Eisen(lll)fluorid, Eisen(ll)ethoxid, Eisen(ll)gluconat, Eisen(ll)nitrat, Eisen(lll)nitrat, Eisen(ll)acetat, FeS04, Fe2(S04)3, Eisen(ll)oxalat, Eisen(ll)citrat, Eisen(lll)citrat, Eisen(lll)acetylacetonat, Eisen(ll)lactat, Eisen(lll)lactat und Eisenchlorid, beispielsweise FeC und wasserhaltigem Eisen(lll)chlorid. In one embodiment of the present invention, water-soluble iron compound (D1) is selected from ammonium iron (II) sulfate, ammonium iron (III) sulfate, ammonium iron (II) citrate, ammonium iron (III) citrate, iron (II) bromide, iron (III ) bromide, iron (II) fluoride, iron (III) fluoride, iron (II) ethoxide, iron (II) gluconate, iron (II) nitrate, iron (III) nitrate, iron (II) acetate, FeSO 4 , Fe 2 ( S0 4 ) 3, iron (II) oxalate, iron (II) citrate, iron (III) citrate, iron (III) acetylacetonate, iron (II) lactate, iron (III) lactate and iron chloride, for example FeC and hydrous iron (III )chloride.
In einer Ausführungsform der vorliegenden Erfindung wählt man wasserunlösliche Eisenverbindung (D2) aus Fe(OH)3, FeOOH, Fe203-aq, FeO, Fe203, Fe304, FeS, Eisen(ll)phosphat In one embodiment of the present invention, water-insoluble iron compound (D2) is selected from Fe (OH) 3 , FeOOH, Fe 2 O 3 -aq, FeO, Fe 2 O 3 , Fe 3 O 4 , FeS, Iron (II) phosphate
(Fe3(P04)2), Eisen(lll)phosphat (FeP04), Eisen(ll)pyrophosphat, Eisen(lll)pyrophosphat, Eisen- carbid, Eisenphosphid, Eisen(ll)phosphonat, Eisen(lll)phosphonat, und Eisencarbonat, bevor- zugt sind Fe(OH)3, FeOOH, Fe2Ü3, Fe304, Eisenphosphat und Eisen(ll)carbonat. Dabei kann man Eisenverbindung (D1 ) und (D2) jeweils aus wasserfreien und wasserhaltigen Eisenverbindungen wählen, beispielsweise den Hydraten. Dabei sollen unter Hydraten nicht nur Monohydrate, sondern auch andere Hydrate verstanden werden, beispielsweise im Falle des Eisen(ll)phosphats auch das Octahydrat. (Fe 3 (PO 4 ) 2), iron (III) phosphate (FePO 4 ), iron (II) pyrophosphate, iron (III) pyrophosphate, iron carbide, iron phosphide, iron (II) phosphonate, iron (III) phosphonate, and iron carbonate, are Trains t forthcoming Fe (OH) 3, FeOOH, Fe2Ü 3, Fe 3 0 4, iron phosphate and iron (II) carbonate. In this case, iron compound (D1) and (D2) can each be selected from anhydrous and hydrous iron compounds, for example the hydrates. Hydrates should not only be understood as meaning monohydrates but also other hydrates, for example in the case of iron (II) phosphate also octahydrate.
In einer Ausführungsform der vorliegenden Erfindung wählt man wasserunlösliche Eisenverbindung (D2) aus Eisenpentacarbonyl. In one embodiment of the present invention, water-insoluble iron compound (D2) is selected from iron pentacarbonyl.
Ausgangsmaterial (D1 ) kann man beispielsweise als wässrige Lösung oder als Pulver einsetzen, beispielsweise mit mittleren Partikeldurchmessern (D50) im Bereich von 10 bis 750 nm, bevorzugt im Bereich von 25 bis 500 nm. Ausgangsmaterial (D2) kann man beispielsweise als wässrige Suspension oder als Pulver einsetzen, beispielsweise mit mittleren Primärpartikeldurchmessern (D50) im Bereich von 10 bis 750 nm, bevorzugt im Bereich von 25 bis 500 nm. Starting material (D1) can be used, for example, as an aqueous solution or as a powder, for example with average particle diameters (D50) in the range from 10 to 750 nm, preferably in the range from 25 to 500 nm. Starting material (D2) can be used, for example, as an aqueous suspension or as powder, for example with average primary particle diameters (D50) in the range of 10 to 750 nm, preferably in the range of 25 to 500 nm.
In einer Ausführungsform der vorliegenden Erfindung kann Ausgangsmaterial (D2) in Form von Agglomeraten vorliegen. In one embodiment of the present invention, starting material (D2) may be in the form of agglomerates.
In einer speziellen Ausführungsform der vorliegenden Erfindung wählt man als Kohlenstoffquelle (C) und Eisenverbindung (D1 ) jeweils Eisenacetat, Eisencitrat, Eisengluconat, Eisenethoxid, oder Ammoniumeisencitrat, d.h. die Eisenverbindung (D1 ) Eisen(ll)acetat, Ei- sen(ll)acetylacetonat, Eisen(ll)citrat, Eisen(ll)lactat, Eisen(lll)lactat, Ammoniumeisen(ll)citrat, Eisen(lll)acetat, Eisen(lll)acetylacetonat, Eisen(lll)citrat bzw. Ammoniumeisen(lll)citrat kann gleichzeitig als Kohlenstoffquelle (C) dienen. In a specific embodiment of the present invention, the carbon source (C) and iron compound (D1) are each selected from iron acetate, iron citrate, iron gluconate, iron ethoxide, or ammonium iron citrate, i. the iron compound (D1) iron (II) acetate, iron (II) acetylacetonate, iron (II) citrate, iron (II) lactate, iron (III) lactate, ammonium iron (II) citrate, iron (III) acetate, iron (III) acetylacetonate, iron (III) citrate or ammonium iron (III) citrate can simultaneously serve as carbon source (C).
In einer speziellen Ausführungsform der vorliegenden Erfindung wählt man als Kohlenstoffquel- le (C) und Eisenverbindung (D2) jeweils Eisencarbid. In a specific embodiment of the present invention, the carbon source (C) and iron compound (D2) are each chosen to be iron carbide.
In einer speziellen Ausführungsform der vorliegenden Erfindung wählt man als Eisenverbindung (D1 ), Kohlenstoffquelle (C) und Lithiumverbindung (B) Lithiumeisencitrat, d.h. Lithiumeisencitrat kann jeweils gleichzeitig als Eisenverbindung (D1 ), Kohlenstoffquelle (C) und als Lithiumverbin- dung (B) dienen. In a specific embodiment of the present invention, as iron compound (D1), carbon source (C) and lithium compound (B), lithium iron citrate, i. Lithium iron citrate can in each case simultaneously serve as iron compound (D1), carbon source (C) and as lithium compound (B).
In einer Ausführungsform der vorliegenden Erfindung wählt man Eisenverbindung (D1 ) und Eisenverbindung (D2) in einem Molverhältnis von 1 : 1 bis 1 : 9, bevorzugt bis 15 : 85, wobei das Molverhältnis auf Fe in Eisenverbindung (D1 ) bzw. Eisenverbindung (D2) (bzw. elementares Eisen) bezogen ist. In one embodiment of the present invention, iron compound (D1) and iron compound (D2) are selected in a molar ratio of from 1: 1 to 1: 9, preferably to 15: 85, the molar ratio to Fe in iron compound (D1) and iron compound (D2 ) (or elemental iron) is related.
In einer Ausführungsform der vorliegenden Erfindung setzt man eine Eisenverbindung (D1 ) und zwei Eisenverbindungen (D2) ein. In einer anderen Ausführungsform der vorliegenden Erfindung setzt man eine Eisenverbindung (D2) und zwei Eisenverbindungen (D1 ) ein. In one embodiment of the present invention, an iron compound (D1) and two iron compounds (D2) are used. In another embodiment of the present invention, an iron compound (D2) and two iron compounds (D1) are used.
In einer Ausführungsform der vorliegenden Erfindung setzt man zwei Phosphorverbindungen (A), eine Lithiumverbindung (B), eine Kohlenstoffquelle (C), eine Eisenverbindung (D1 ) und eine Eisenverbindung (D2) ein. In einer bevorzugten Ausführungsform der vorliegenden Erfindung setzt man zwei Phosphorverbindungen (A), eine Lithiumverbindung (B), zwei Kohlenstoffquellen (C), eine Eisenverbindung (D1 ) und eine Eisenverbindung (D2) ein. In one embodiment of the present invention, two phosphorus compounds (A), a lithium compound (B), a carbon source (C), an iron compound (D1) and an iron compound (D2) are used. In a preferred embodiment of the present invention, two phosphorus compounds (A), one lithium compound (B), two carbon sources (C), an iron compound (D1) and an iron compound (D2) are used.
In einer bevorzugten Ausführungsform der vorliegenden Erfindung setzt man zwei Phosphorverbindungen (A), eine Lithiumverbindung (B), zwei Kohlenstoffquellen (C), eine Eisenverbindung (D1 ) und eine Eisenverbindung (D2) ein, wobei Eisenverbindung (D1 ) ein Salz einer organischen Verbindung ist und als eine der Kohlenstoffquellen (C) dient. In a preferred embodiment of the present invention, two phosphorus compounds (A), one lithium compound (B), two carbon sources (C), an iron compound (D1) and an iron compound (D2) are used, and iron compound (D1) is a salt of an organic compound is and serves as one of the carbon sources (C).
In einer Ausführungsform der vorliegenden Erfindung kann man in Schritt (a) eine oder mehrere reduzierende Verbindungen einsetzen, beispielsweise kann man ein oder mehrere Reduktionsmittel (E) einsetzen. Diese Ausführungsform ist dann bevorzugt, wenn man mindestens eine Eisenverbindung (D1 ) oder (D2) einsetzt, in der Fe in der Oxidationsstufe +3 vorliegt. Als redu- zierende Verbindungen sind beispielsweise solche Phosphorverbindungen (A) geeignet, in denen P in der Oxidationsstufe +3 oder +1 vorliegt, insbesondere Phosphorige Säure (H3PO3), Hypophosphorige Säure (H3PO2) und ihre jeweiligen Ammonium- und Lithiumsalze sowie Ester, beispielsweise Ci-Cio-Alkylester. Als Reduktionsmittel (E) ist weiterhin elementares Eisen geeignet. In one embodiment of the present invention, one or more reducing compounds may be used in step (a), for example one or more reducing agents (E) may be employed. This embodiment is preferred if at least one iron compound (D1) or (D2) is used in which Fe is present in the oxidation state +3. Examples of suitable reducing compounds are those phosphorus compounds (A) in which P is in the +3 or +1 oxidation state, in particular phosphorous acid (H3PO3), hypophosphorous acid (H3PO2) and their respective ammonium and lithium salts, and also esters, for example Ci-Cio-alkyl esters. As reducing agent (E) elemental iron is also suitable.
Als Reduktionsmittel (E) kann man gasförmige, flüssige oder feste Substanzen einsetzen, die unter den Bedingungen von Schritt (a) oder (b) Eisen, soweit erforderlich, in die Oxidationsstufe +2 überführen. In einer Ausführungsform der vorliegenden Erfindung wählt man als festes Reduktionsmittel (E) ein Metall, beispielsweise Nickel oder Mangan, oder ein Metallhydrid. As reducing agent (E) it is possible to use gaseous, liquid or solid substances which, under the conditions of step (a) or (b), convert iron, if necessary, into the oxidation state +2. In one embodiment of the present invention, a solid reducing agent (E) is selected from a metal, for example nickel or manganese, or a metal hydride.
Als gasförmige Reduktionsmittel (E) kann man beispielsweise Wasserstoff, Kohlenmonoxid, Ammoniak und/oder Methan einsetzen. Wenn man ein oder mehrere gasförmige Reduktions- mittel (E) einzusetzen wünscht, so ist es bevorzugt, das oder die gasförmigen Reduktionsmittel (E) in Schritt (b) einzusetzen, der unten weiter erläutert wird. As gaseous reducing agent (E) can be used for example hydrogen, carbon monoxide, ammonia and / or methane. If it is desired to use one or more gaseous reducing agents (E), it is preferred to use the gaseous reducing agent (E) in step (b), which is further explained below.
Weitere geeignete Reduktionsmittel (E) sind metallisches Eisen und Eisenpentacarbonyl. In einer anderen Ausführungsform der vorliegenden Erfindung setzt man keine Reduktionsmittel (E) ein. Other suitable reducing agents (E) are metallic iron and iron pentacarbonyl. In another embodiment of the present invention, no reducing agents (E) are used.
In einer Ausführungsform der vorliegenden Erfindung wählt man in Schritt (a) die Mengenverhältnisse von Eisenverbindungen (D1 und (D2), an Phosphorverbindung(en) (A) und Lithium- verbindung(en) (B) so, dass die gewünschte Stöchiometrie einer Eisenverbindung erfüllt ist, die man als Elektrodenmaterial einzusetzen gedenkt. So kann man in Schritt (a) die Mengenverhältnisse von Eisenverbindungen (D1 und (D2), an Phosphorverbindung(en) (A) und Lithium- verbindung(en) (B) so wählen, dass die Stöchiometrie beispielsweise Li3Fe2(P04)3, Li2Fe2(P04)2, Li4Fe(P04)2 oder Li2FeP2Ü7 oder insbesondere LiFeP04 ergibt. In one embodiment of the present invention, in step (a), the proportions of iron compounds (D1 and (D2), phosphorus compound (s) (A) and lithium compound (s) (B) are chosen so that the desired stoichiometry of an iron compound In step (a), the proportions of iron compounds (D1 and (D2), phosphorus compound (s) (A) and lithium Select compound (s) (B) such that the stoichiometry yields, for example, Li 3 Fe 2 (PO 4 ) 3, Li 2 Fe 2 (PO 4 ) 2, Li 4 Fe (PO 4 ) 2 or Li 2 FeP 2 O 7 or in particular LiFePO 4 .
Als Ausgangsmaterial (F) kann man mindestens eine weitere Metallverbindung einsetzen, in der das oder die Metalle von Eisen verschieden sind, kurz auch Metallverbindung (F) genannt. Dabei wird als Metall vorzugsweise ein oder mehrere Metalle aus der ersten Periode der Übergangsmetalle gewählt. Besonders bevorzugt wählt man Metallverbindung (F) aus Verbindungen von Ti, V, Cr, Mn, Co, Ni, Mg, AI, Nb, W, Mo, Cu und Zn, insbesondere aus Verbindungen von Sc, Ti, V, Mn, Ni und Co. Ganz besonders bevorzugt wählt man Metallverbindung (F) aus Oxi- den, Hydroxiden, Carbonaten und Sulfaten von Metallen der ersten Periode der Übergangsmetalle. As starting material (F) it is possible to use at least one further metal compound in which the one or more metals are different from iron, in short also called metal compound (F). In this case, it is preferable to use one or more metals from the first period of the transition metals as the metal. Particular preference is given to choosing metal compound (F) from compounds of Ti, V, Cr, Mn, Co, Ni, Mg, Al, Nb, W, Mo, Cu and Zn, in particular compounds of Sc, Ti, V, Mn, Ni and Co. Very particular preference is given to choosing metal compound (F) from oxides, hydroxides, carbonates and sulfates of metals of the first period of the transition metals.
Metallverbindung (F) kann wasserfrei oder wasserhaltig sein. Metallkation in Metallverbindung (F) kann in komplexierter Form vorliegen, beispielsweise als Hydratkomplex, oder unkomple- xiert sein. Metal compound (F) may be anhydrous or hydrous. Metal cation in metal compound (F) can be present in complexed form, for example as hydrate complex, or uncomplexed.
Bei Metallverbindung (F) kann es sich um ein Salz handeln, beispielsweise Halogenid, insbesondere Chlorid, weiterhin Nitrat, Carbonat, Sulfat, Oxid, Hydroxid, Acetat, Citrat, Tartrat, Oxalat oder Acetylacetonat, oder um Salze mit verschiedenen Anionen. Vorzugsweise werden Salze gewählt aus Oxiden, Carbonaten, Hydroxiden und Nitraten, basisch oder neutral. Ganz besonders bevorzugte Beispiele für Metallverbindungen (F) sind Oxide, Hydroxide, Carbonate und Sulfate. Metal compound (F) can be a salt, for example halide, in particular chloride, furthermore nitrate, carbonate, sulfate, oxide, hydroxide, acetate, citrate, tartrate, oxalate or acetylacetonate, or salts with different anions. Preferably, salts are selected from oxides, carbonates, hydroxides and nitrates, basic or neutral. Very particularly preferred examples of metal compounds (F) are oxides, hydroxides, carbonates and sulfates.
In einer anderen Ausführungsform der vorliegenden Erfindung wählt man Metallverbindung (F) aus Fluoriden, beispielsweise als Alkalimetallfluorid, insbesondere Natriumfluorid. In another embodiment of the present invention, metal compound (F) is selected from fluorides, for example as alkali metal fluoride, especially sodium fluoride.
In einer Ausführungsform der vorliegenden Erfindung kann Metallverbindung (F) als eine oder die einzige Kohlenstoffquelle (C) wirken, beispielhaft seien Nickelacetat, Kobaltacetat, In one embodiment of the present invention, metal compound (F) may act as one or the sole carbon source (C), for example nickel acetate, cobalt acetate,
Zinkacetat und Mangan(ll)acetat genannt. Called zinc acetate and manganese (II) acetate.
In einer Ausführungsform der vorliegenden Erfindung kann Metallverbindung (F) als ein oder das einzige Reduktionsmittel (E) wirken. Beispielhaft seien Mangan(ll)acetat, MnC03, MnS04, Nickellactat, Manganhydrid, Nickelhydrid, Nickelsuboxid, Nickelcarbid, Mangancarbid und Man- gan(ll)lactat genannt. In one embodiment of the present invention, metal compound (F) may act as one or the sole reducing agent (E). Examples which may be mentioned are manganese (II) acetate, MnCO 3, MnSO 4 , nickel lactate, manganese hydride, nickel hydride, nickel suboxide, nickel carbide, manganese carbide and manganese (II) lactate.
Erfindungsgemäß werden die Komponenten (A) bis (D2) in Gegenwart von Wasser miteinander vermischt. Unter der Gegenwart von Wasser wird insbesondere verstanden, dass bevorzugt mindestens 20 Gew.-%, besonders bevorzugt mindestens 40 Gew.-%, insbesondere mindes- tens 60 Gew.-% Wasser jeweils bezogen auf die Gesamtmasse der Komponenten (A) bis (D2) und Wasser eingesetzt wird. Meist wird nicht mehr als 90 Gew.-% Wasser bezogen auf die Gesamtmasse der Komponenten (A) bis (D2) und Wasser eingesetzt. In einer Variante setzt man Wasser und organisches Lösungsmittel (G) zu. Beispiele für geeignete organische Lösungsmittel sind insbesondere halogenfreie organische Lösungsmittel (G) wie Methanol, Ethanol, Isopropanol oder n-Hexan, Cyclohexan, Aceton, Ethylacetat, Di- ethylether und Diisopropylether. Sofern organisches Lösungsmittel mit verwendet wird, ist es bevorzugt in untergeordneten Mengen enthalten. Im Allgemeinen beträgt der Anteil an organischem Lösungsmittel nicht mehr als 5 Gew.-% bezogen auf die Menge Wasser. Bevorzugt liegen die Anteile erheblich niedriger, beispielsweise bis zu 2 Gew.-% oder 1 Gew.-%. Oft ist der Anteil an organischem Lösungsmittel nur im Bereich auftretender Verunreinigungen von Was- ser. According to the invention, the components (A) to (D2) are mixed together in the presence of water. The presence of water is understood in particular to mean that preferably at least 20% by weight, particularly preferably at least 40% by weight, in particular at least 60% by weight of water, based in each case on the total mass of components (A) to (D2 ) and water is used. In most cases not more than 90% by weight of water, based on the total mass of components (A) to (D2) and water, is used. In one variant, water and organic solvent (G) are added. Examples of suitable organic solvents are in particular halogen-free organic solvents (G) such as methanol, ethanol, isopropanol or n-hexane, cyclohexane, acetone, ethyl acetate, diethyl ether and diisopropyl ether. If organic solvent is used with, it is preferably contained in minor amounts. In general, the content of organic solvent is not more than 5% by weight based on the amount of water. Preferably, the proportions are considerably lower, for example up to 2 wt .-% or 1 wt .-%. Often, the proportion of organic solvent is only in the range of occurring impurities of water.
Bevorzugt ist, in Schritt (a) Wasser, aber keine organischen Lösungsmittel (G) einzusetzen. Wasser verschiedener Qualitäten kann verwendet werden. Insbesondere wird aufgereinigtes, bevorzugt vollentsalztes Wasser eingesetzt. It is preferred to use water in step (a) but no organic solvents (G). Water of different qualities can be used. In particular, purified, preferably demineralized water is used.
Ohne dass einer bestimmten Theorie der Vorzug gegeben werden soll, ist es möglich, dass gewisse organische Lösungsmittel (G) wie sekundäre oder primäre Alkanole auch als Reduktionsmittel (E) wirken können. Das Vermischen in Schritt (a) kann man beispielsweise durch Verrühren von einer oder mehreren Suspensionen der Ausgangsmaterialen (A) bis (D2) und gegebenenfalls (E), (F) und (G) durchführen. In anderen Ausführungsformen vermischt man die Ausgangsmaterialen (A) bis (D) und gegebenenfalls (E) und (F) als Feststoffe miteinander innig. In einer anderen Ausführungsform der vorliegenden Erfindung kann man die Ausgangsmaterialen (A) bis (D2) und gegebe- nenfalls (E) und (F) und (G) miteinander zu einer Paste verkneten. Without wishing to prioritize any particular theory, it is possible that certain organic solvents (G), such as secondary or primary alkanols, may also act as reducing agents (E). The mixing in step (a) can be carried out, for example, by stirring one or more suspensions of the starting materials (A) to (D2) and optionally (E), (F) and (G). In other embodiments, the starting materials (A) to (D) and optionally (E) and (F) are intimately mixed together as solids. In another embodiment of the present invention, the starting materials (A) to (D2) and, if appropriate, (E) and (F) and (G) may be kneaded together to form a paste.
In einer Ausführungsform der vorliegenden Erfindung führt man das Vermischen in Schritt (a) bei Temperaturen im Bereich von null bis 200°C durch, bevorzugt führt man es bei Temperaturen im Bereich der Raumtemperatur bis zu 1 10°C durch, besonders bevorzugt bis 80°C. In one embodiment of the present invention, the mixing in step (a) is carried out at temperatures in the range from zero to 200 ° C, preferably it is carried out at temperatures in the range of room temperature up to 1 10 ° C, particularly preferably up to 80 ° C.
In einer Ausführungsform der vorliegenden Erfindung führt man das Vermischen in Schritt (a) bei Normaldruck durch. In anderen Ausführungsformen führt man das Vermischen bei erhöhtem Druck durch, beispielsweise bei 1 ,1 bis zu 20 bar. In anderen Ausführungsformen führt man das Vermischen in Schritt (a) bei reduziertem Druck durch, beispielsweise bei 10 mbar bis zu 990 mbar. In one embodiment of the present invention, the mixing in step (a) is carried out under atmospheric pressure. In other embodiments, the mixing is carried out at elevated pressure, for example at 1, 1 up to 20 bar. In other embodiments, the mixing in step (a) is carried out under reduced pressure, for example at 10 mbar up to 990 mbar.
Das Vermischen in Schritt (a) kann man über einen Zeitraum im Bereich von einer Minute bis zu 12 Stunden durchführen, bevorzugt sind 15 Minuten bis 4 Stunden, besonders bevorzugt 20 Minuten bis 2 Stunden. The mixing in step (a) can be carried out over a period in the range of one minute to 12 hours, preferred are 15 minutes to 4 hours, more preferably 20 minutes to 2 hours.
In einer Ausführungsform der vorliegenden Erfindung führt man das Vermischen in Schritt (a) in einer Stufe durch. In einer anderen Ausführungsform führt man das Vermischen in Schritt (a) in zwei oder mehr Stufen durch. So ist es beispielsweise möglich, zunächst Eisenverbindung (D1 ) und Lithiumverbindung (B) gemeinsam in Wasser zu lösen bzw. zu suspendieren, danach mit Phosphorver- bindung (A) und Kohlenstoffquelle (C) sowie Eisenverbindung (D2) zu vermischen und danach gegebenenfalls mit Reduktionsmittel (E) und/oder weiterer Metallverbindung (F) zu vermischen. In one embodiment of the present invention, the mixing in step (a) is performed in one step. In another embodiment, the mixing in step (a) is carried out in two or more stages. Thus, it is possible, for example, first to dissolve or suspend iron compound (D1) and lithium compound (B) together in water, then to mix with phosphorus compound (A) and carbon source (C) and iron compound (D2) and then optionally with Reducing agent (E) and / or other metal compound (F) to mix.
In einer Ausführungsform legt man zunächst Wasser und/oder organisches Lösungsmittel vor, versetzt dann mit nacheinander mit Lithiumverbindung (B), Eisenverbindung (D1 ) und Eisen- Verbindung (D2), Phosphor oder Phosphorverbindung (C), Kohlenstoffquelle (B) und gegebenenfalls mit Reduktionsmittel (E) und/oder weiterer Metallverbindung (F). In one embodiment, water and / or organic solvent are initially added, followed by sequential addition with lithium compound (B), iron compound (D1) and iron compound (D2), phosphorus or phosphorus compound (C), carbon source (B) and optionally with Reducing agent (E) and / or further metal compound (F).
Durch Schritt (a) erhält man eine Mischung von mindestens einer Phosphorverbindung (A), mindestens einer Lithiumverbindung (B), mindestens einer Kohlenstoffquelle (C), mindestens einer Eisenverbindung (D1 ), mindestens einer Eisenverbindung (D2), gegebenenfalls Reduktionsmittel (E), gegebenenfalls weiterer Metallverbindung (F), Wasser und gegebenenfalls organischem Lösungsmittel (G) in pastöser Form, als Wasser-haltiges Pulver, als Suspension oder als Lösung. Vor der eigentlichen thermischen Behandlung nach Schritt (b) kann man Mischung aus Schritt (a) trocknen. Step (a) gives a mixture of at least one phosphorus compound (A), at least one lithium compound (B), at least one carbon source (C), at least one iron compound (D1), at least one iron compound (D2), optionally reducing agent (E) , optionally further metal compound (F), water and optionally organic solvent (G) in pasty form, as a water-containing powder, as a suspension or as a solution. Prior to the actual thermal treatment of step (b), a mixture of step (a) may be dried.
Zum Trocknen kann man beispielsweise so vorgehen, dass man Wasser und gegebenenfalls organisches Lösungsmittel (G) verdampft, beispielsweise durch Abdestillieren, Gefriertrocknen, bevorzugt durch Zerstäubungstrocknen und insbesondere durch Sprühtrocknen. For drying, it is possible, for example, to evaporate water and optionally organic solvent (G), for example by distilling off, freeze-drying, preferably by spray-drying and in particular by spray-drying.
In einer Ausführungsform der vorliegenden Erfindung trocknet man die Mischung aus Schritt (a), beispielsweise mit einem Zerstäubungstrockner. Geeignet sind beispielsweise Zerstäu- bungstrockner mit Scheibenzerstäubern, mit Druckdüsenzerstäubung und solche mit Zweistoff- düsenzerstäubung, insbesondere mit innen mischenden Zweistoffdüsen. In one embodiment of the present invention, the mixture from step (a) is dried, for example with a sputtering dryer. For example, atomizing dryers with disc atomizers, with atomized nozzle atomization and those with two-component atomizing, in particular with internally mixing two-component nozzles, are suitable.
In einer Ausführungsform der vorliegenden Erfindung sprühtrocknet man die Mischung aus Schritt (a) mit Hilfe einer mindestens Apparatur, die sich zum Versprühen mindestens einer Sprühdüse bedient, d.h. man führt eine Sprühtrocknung oder Zerstäubungstrocknung durch. Die Sprühtrocknung kann man in einem Sprühtrockner durchführen. Geeignete Sprühtrockner sind Trockentürme, beispielsweise Trockentürme mit einer oder mehreren Zerstäubungsdüsen und Sprühtrockner mit integriertem Wirbelbett. In one embodiment of the present invention, the mixture of step (a) is spray-dried by means of an at least apparatus which operates to spray at least one spray nozzle, i. one carries out a spray drying or spray drying. The spray drying can be carried out in a spray dryer. Suitable spray dryers are drying towers, for example drying towers with one or more atomizing nozzles and spray dryer with integrated fluidized bed.
Besonders bevorzugte Düsen sind Zweistoffdüsen (englisch: two phase nozzles), also Düsen, in deren Innerem oder an deren Mündungen mittels getrennter Zugänge Stoffe verschiedenen Aggregatzustandes intensiv vermischt gebracht werden. Weitere Beispiele für geeignete Düsen sind Kombidüsen, beispielsweise Kombinationen von Zweistoff- und Druckdüsen. Particularly preferred nozzles are two-phase nozzles (English: two-phase nozzles), ie nozzles in the interior or at the mouths by means of separate approaches different substances Physical state can be brought intensively mixed. Further examples of suitable nozzles are combination nozzles, for example combinations of binary and pressure nozzles.
Zur Durchführung der Trocknung kann man so vorgehen, dass man in einer Variante die in Schritt (a) erhaltene Mischung durch eine oder mehrere Sprüheinrichtungen presst, beispielsweise durch eine oder mehrere Düsen oder in einen Heißluftstrom oder in einen heißen Inertgasstrom oder heiße Brennerabgase, wobei der Heißgasstrom bzw. der heiße Inertgasstrom oder die heißen Brennerabgase eine Temperatur im Bereich von 170 bis 550°C haben kann, bevorzugt 200 bis 350°C, insbesondere 250 bis 330°C. Dadurch wird die Mischung innerhalb von Bruchteilen einer Sekunde oder innerhalb von wenigen Sekunden zu einem Trockengut getrocknet, das vorzugsweise als Pulver anfällt. Das anfallende Pulver kann eine gewisse Restfeuchte aufweisen, beispielsweise im Bereich von 500 ppm bis 10 Gew.-%, bevorzugt im Bereich von 1 bis 8 Gew.-%, besonders bevorzugt im Bereich von 2 bis 6 Gew.-%. Die Ausgangstemperatur des Gasstroms kann beispielsweise im Bereich 90 bis 190°C liegen, bevorzugt 1 10 bis 170°C, insbesondere 125 bis 150°C. To carry out the drying, it is possible to proceed in a variant by pressing the mixture obtained in step (a) through one or more spraying devices, for example through one or more nozzles or into a hot air stream or into a hot inert gas stream or hot burner exhaust gases Hot gas stream or the hot inert gas stream or the hot burner exhaust gases may have a temperature in the range of 170 to 550 ° C, preferably 200 to 350 ° C, in particular 250 to 330 ° C. As a result, the mixture is dried within a fraction of a second or within a few seconds to a dry material, which is preferably obtained as a powder. The resulting powder may have a certain residual moisture, for example in the range of 500 ppm to 10 wt .-%, preferably in the range of 1 to 8 wt .-%, particularly preferably in the range of 2 to 6 wt .-%. The starting temperature of the gas stream may be for example in the range 90 to 190 ° C, preferably 1 10 to 170 ° C, in particular 125 to 150 ° C.
In einer bevorzugten Ausführungsform wählt man die Temperatur des Heißluftstroms bzw. des heißen Inertgasstroms bzw. der heißen Brennerabgase so, dass sie oberhalb der Temperatur in Schritt (a) liegt. In a preferred embodiment, the temperature of the hot air stream or of the hot inert gas stream or of the hot burner exhaust gases is selected such that it lies above the temperature in step (a).
In einer Ausführungsform der vorliegenden Erfindung strömt der Heißluftstrom oder der heiße Inertgasstrom oder die heißen Brennerabgase in Richtung mit der eingebrachten Mischung aus Schritt (a) (Gleichstromverfahren). In einer anderen Ausführungsform der vorliegenden Erfin- dung strömt der Heißluftstrom oder heiße Inertgasstrom die heißen Brennerabgase in Gegenrichtung zur eingebrachten Mischung aus Schritt (a) (Gegenstromverfahren). Die Sprüheinrichtung befindet vorzugsweise sich am oberen Teil des Sprühtrockners, insbesondere des Sprühturms. Anfallendes Trockengut kann man im Anschluss an die eigentliche Sprühtrocknung durch einen Abscheider, beispielsweise einen Zyklon vom Heißluftstrom bzw. heißen Inertgasstrom bzw. von den heißen Brennerabgasen abtrennen. In einer anderen Ausführungsform trennt man angefallenes Trockengut im Anschluss an die eigentliche Sprühtrocknung durch einen oder mehrere Filter vom Heißluftstrom bzw. heißen Inertgasstrom bzw. von den heißen Brennerabgasen ab. In one embodiment of the present invention, the hot air stream or the hot inert gas stream or the hot burner exhaust gases flow in the direction of the introduced mixture from step (a) (DC method). In another embodiment of the present invention, the hot air stream or hot inert gas stream flows the hot burner exhaust gases in the opposite direction to the introduced mixture from step (a) (countercurrent process). The spraying device is preferably located at the upper part of the spray dryer, in particular the spray tower. Resulting dry material can be separated after the actual spray drying by a separator, such as a cyclone from the hot air stream or hot inert gas or from the hot burner exhaust gases. In another embodiment, incurred dry material after the actual spray drying separated by one or more filters from the hot air flow or hot inert gas or from the hot burner exhaust gases.
Trockengut kann beispielsweise einen mittleren Partikeldurchmesser (D50, Gewichtsmittel) im Bereich von 1 bis 50 μηη aufweisen. Bevorzugt ist dabei, wenn der mittlere Partikeldurchmesser (D99), (bestimmt als Volumenmittel) bis zu 120 μηη beträgt, besonders bevorzugt bis zu 50 μηη und ganz besonders bevorzugt bis zu 20 μηη. Dry material can, for example, have an average particle diameter (D50, weight average) in the range from 1 to 50 μm. It is preferred if the average particle diameter (D99), (determined as volume average) up to 120 μηη, more preferably up to 50 μηη and most preferably up to 20 μηη.
Die Trocknung kann man absatzweise (diskontinuierlich) oder auch kontinuierlich durchführen. In Schritt (b) des erfindungsgemäßen Verfahrens behandelt man die Mischung aus Schritt (a) bzw. das Trockengut thermisch, und vorzugsweise zwar bei Temperaturen im Bereich von 350 bis 1200°C, bevorzugt 400 bis 900°C. The drying can be carried out batchwise (batchwise) or else continuously. In step (b) of the process according to the invention, the mixture from step (a) or the dry matter is treated thermally, and preferably at temperatures in the range from 350 to 1200 ° C., preferably from 400 to 900 ° C.
In einer Ausführungsform der vorliegenden Erfindung führt man die thermische Behandlung in Schritt (b) in einem Temperaturprofil mit zwei bis fünf, bevorzugt mit drei oder vier Zonen durch, wobei jede Zone des Temperaturprofils vorzugsweise eine höhere Temperatur aufweist als die vorgehende. Beispielsweise kann man in einer ersten Zone eine Temperatur im Bereich von 350 bis 550°C einstellen, in einer zweiten Zone im Bereich von 450 bis 750°C, wobei die Temperatur höher ist als in der ersten Zone. Wünscht man eine dritte Zone einzuführen, so kann man in der dritten Zone bei 700 bis 1200°C thermisch behandeln, aber in jedem Falle bei einer Temperatur, die höher ist als in der zweiten Zone. Die Zonen kann man beispielsweise durch das Einstellen bestimmter Heizzonen erzeugen. In one embodiment of the present invention, the thermal treatment in step (b) is carried out in a temperature profile with two to five, preferably with three or four zones, wherein each zone of the temperature profile preferably has a higher temperature than the preceding one. For example, in a first zone, a temperature in the range of 350 to 550 ° C can be set, in a second zone in the range of 450 to 750 ° C, the temperature being higher than in the first zone. If you wish to introduce a third zone, you can thermally treat in the third zone at 700 to 1200 ° C, but in any case at a temperature higher than in the second zone. The zones can be created, for example, by setting certain heating zones.
Wünscht man Schritt (b) absatzweise durchzuführen, so kann man ein zeitliches Temperaturprofil einstellen, d. h. man behandelt beispielsweise zunächst bei 350 bis 550°C, dann bei 450 bis 750°C, wobei die Temperatur höher ist als in der ersten Phase. Wünscht man eine dritte Phase einzuführen, so kann man in der dritten Phase bei 700 bis 1200°C thermisch behandeln, aber in jedem Falle bei einer Temperatur, die höher ist als in der zweiten Phase. If one wishes to carry out step (b) intermittently, one can set a temporal temperature profile, ie. H. For example, it is first treated at 350 to 550 ° C, then at 450 to 750 ° C, the temperature being higher than in the first phase. If you wish to introduce a third phase, you can treat in the third phase at 700 to 1200 ° C, but in any case at a temperature that is higher than in the second phase.
Die thermische Behandlung gemäß Schritt (b) kann man beispielsweise in einem Drehrohrofen, einem Durchschiebeofen oder RHK (englisch roller-hearth-kiln), einem Pendelreaktor, einem Muffelofen, einem Kalzinationsofen oder einem Quarzkugelofen durchführen. The thermal treatment according to step (b) can be carried out, for example, in a rotary kiln, a push-through furnace or RHK (English roller-hearth-kiln), a pendulum reactor, a muffle furnace, a calcination furnace or a quartz ball furnace.
Die thermische Behandlung gemäß Schritt (b) kann man beispielsweise in einer schwach oxi- dierenden Atmosphäre, bevorzugt in inerter oder reduzierender Atmosphäre durchführen. The thermal treatment according to step (b) can be carried out, for example, in a weakly oxidizing atmosphere, preferably in an inert or reducing atmosphere.
Unter schwach oxidierend wird dabei im Rahmen der vorliegenden Erfindung eine Sauerstoff- haltige Stickstoffatmosphäre verstanden, die bis zu 2 Vol.-% Sauerstoff enthält, bevorzugt bis zu 1 Vol.-%. Weakly oxidizing means in the context of the present invention an oxygen-containing nitrogen atmosphere which contains up to 2% by volume of oxygen, preferably up to 1% by volume.
Beispiele für inerte Atmosphäre sind Edelgas-, insbesondere Argonatmosphäre, und Stickstoffatmosphäre. Beispiele für eine reduzierende Atmosphäre sind Stickstoff oder Edelgase, die 0,1 bis 10 Vol.-% Kohlenmonoxid, Ammoniak, Wasserstoff oder Kohlenwasserstoff enthalten, insbesondere Methan. Weitere Beispiele für eine reduzierende Atmosphäre sind Luft oder mit Stickstoff oder mit Kohlendioxid angereicherte Luft, die jeweils mehr mol-% Kohlenmonoxid, Wasserstoff oder Kohlenwasserstoff enthalten als Sauerstoff. In einer Ausführungsform der vorliegenden Erfindung kann man Schritt (b) über einen Zeitraum im Bereich von 1 Minute bis zu 24 Stunden, bevorzugt im Bereich von 10 Minuten bis 3 Stunden durchführen. Das erfindungsgemäße Verfahren lässt sich ohne große Staubbelastung durchführen. Durch das erfindungsgemäße Verfahren sind Elektrodenmaterialien mit vorzüglichen rheologischen Eigenschaften zugänglich, die sich als Elektrodenmaterialien eignen und sehr gut verarbeiten lassen. Beispielsweise lassen sie sich zu Pasten mit guten rheologischen Eigenschaften verarbeiten, derartige Pasten haben eine geringere Viskosität. Examples of inert atmosphere are noble gas, in particular argon atmosphere, and nitrogen atmosphere. Examples of a reducing atmosphere are nitrogen or noble gases containing 0.1 to 10% by volume of carbon monoxide, ammonia, hydrogen or hydrocarbon, especially methane. Further examples of a reducing atmosphere are air or air enriched with nitrogen or with carbon dioxide, each containing more mol% of carbon monoxide, hydrogen or hydrocarbon than oxygen. In one embodiment of the present invention, step (b) may be carried out over a period of time in the range of 1 minute to 24 hours, preferably in the range of 10 minutes to 3 hours. The inventive method can be carried out without much dust. By the method according to the invention electrode materials with excellent rheological properties are accessible, which are suitable as electrode materials and can be processed very well. For example, they can be processed into pastes with good rheological properties, such pastes have a lower viscosity.
Nach dem erfindungsgemäßen Verfahren hergestellte Materialien zeichnen sich durch sehr gute Ratenfähigkeit aus, also sehr guter Kapazität bei hoher Entladegeschwindigkeit. Sie sind daher zum Betreiben von Geräten wie beispielsweise Bohrern und Akkubohrschraubern sehr gut geeignet. Materials produced by the process according to the invention are characterized by very good rate capability, ie very good capacity at high discharge rates. They are therefore very suitable for operating devices such as drills and Akkubohrschraubern.
Ein weiterer Gegenstand der vorliegenden Erfindung sind Elektrodenmaterialien in partikulärer Form, enthaltend Agglomerate von Primärpartikeln, wobei die Agglomerate enthalten i. Primärpartikel von lithiiertem Eisenphosphat mit Olivinstruktur, kurz auch„Primärpartikel (i)" genannt, wobei die Primärpartikel (i) einen mittleren Durchmesser (D50) im Bereich von 20 bis 250 nm, bevorzugt 50 bis 150 nm aufweisen, ii. Primärpartikel von lithiiertem Eisenphosphat mit Olivinstruktur, kurz auch„Primärpartikel (ii)" genannt, wobei die Primärpartikel (ii) einen mittleren Durchmesser (D50) im Bereich von 300 bis 1000, bevorzugt 350 bis 750 nm aufweisen, iii. gegebenenfalls Kohlenstoff in elektrisch leitfähiger Modifikation, kurz auch„Kohlenstoff (iii)" genannt. Another object of the present invention are electrode materials in particulate form, containing agglomerates of primary particles, wherein the agglomerates contain i. Primary particles of lithiated iron phosphate with olivine structure, in short also called "primary particles (i)", wherein the primary particles (i) have an average diameter (D50) in the range of 20 to 250 nm, preferably 50 to 150 nm, ii. Primary particles of lithiated iron phosphate with olivine structure, in short also called "primary particle (ii)", wherein the primary particles (ii) have an average diameter (D50) in the range of 300 to 1000, preferably 350 to 750 nm, iii. optionally carbon in electrically conductive modification, also called "carbon (iii)" for short.
Dabei kann Kohlenstoff (iii) einen mittleren Partikeldurchmesser (D50) (Primärpartikeldurchmesser) im Bereich von 1 bis 500 nm aufweisen, bevorzugt im Bereich von 2 bis 100 nm, besonders bevorzugt im Bereich von 3 bis 50 nm, ganz besonders bevorzugt im Bereich von 4 bis 10 nm. Dabei werden Partikeldurchmesser von Kohlenstoff (iii) im Rahmen der vorliegenden Erfindung bevorzugt als Volumenmittel angegeben, bestimmbar beispielsweise durch XRD- Analyse und durch bildgebende Verfahren wie SEM / TEM. In this case, carbon (iii) can have an average particle diameter (D50) (primary particle diameter) in the range from 1 to 500 nm, preferably in the range from 2 to 100 nm, particularly preferably in the range from 3 to 50 nm, very particularly preferably in the range from 4 In this case, particle diameter of carbon (iii) in the context of the present invention are preferably given as volume average, determinable for example by XRD analysis and by imaging methods such as SEM / TEM.
Den mittleren Durchmesser von Primärpartikeln (i) und Primärpartikeln (ii) lassen sich durch XRD-Analyse und durch bildgebende Verfahren wie REM / TEM nachweisen, die Durchmesser der Sekundärpartikel (ii) beispielsweise durch Laserbeugung an Dispersionen (gasförmig oder flüssig). The average diameter of primary particles (i) and primary particles (ii) can be detected by XRD analysis and by imaging techniques such as SEM / TEM, the diameter of the secondary particles (ii), for example by laser diffraction on dispersions (gaseous or liquid).
In einer Ausführungsform der vorliegenden Erfindung liegen Primärpartikel (i) und Primärpartikel (ii) in Agglomeraten in einem Volumenverhältnis (D50) im Bereich von 1 :9 bis 1 :1 vor. In einer Ausführungsform der vorliegenden Erfindung liegt das Gewichtsverhältnis der Summe von Primärpartikeln (i) und Primärpartikeln (ii) zu Kohlenstoff (iii) im Bereich von 200:1 bis 5:1 , bevorzugt 100 : 1 bis 10 : 1 , besonders bevorzugt 100 : 1 ,5 bis 20 : 1. Kohlenstoff (iii) kann in den Poren von Sekundärpartikeln (Agglomeraten) von Primärpartikeln (i) und Primärpartikeln (ii) oder in Form von Partikeln vorliegen, die Agglomerate von Primärpartikeln (i) und Primärpartikeln (ii) punktförmig oder einen oder mehrere Partikel von Kohlenstoff (iii) kontaktieren können. In einer anderen Ausführungsform der vorliegenden Erfindung kann Kohlenstoff (iii) als Be- schichtung von Agglomeraten von Primärpartikeln (i) und Primärpartikeln (ii) vorliegen, und zwar als komplette Beschichtung oder als partielle Beschichtung. Eine derartige gegebenenfalls partielle Beschichtung kann beispielsweise auch im Inneren von Agglomeraten von Primärpartikeln (i) und Primärpartikeln (ii) vorliegen, also in Poren. In one embodiment of the present invention, primary particles (i) and primary particles (ii) are present in agglomerates in a volume ratio (D50) in the range of 1: 9 to 1: 1. In one embodiment of the present invention, the weight ratio of the sum of primary particles (i) and primary particles (ii) to carbon (iii) is in the range from 200: 1 to 5: 1, preferably 100: 1 to 10: 1, particularly preferably 100: 1, 5 to 20: 1. Carbon (iii) may be present in the pores of secondary particles (agglomerates) of primary particles (i) and primary particles (ii) or in the form of particles containing agglomerates of primary particles (i) and primary particles (ii) punctiform or one or more particles of carbon (iii) can contact. In another embodiment of the present invention, carbon (iii) can be present as a coating of agglomerates of primary particles (i) and primary particles (ii), as a complete coating or as a partial coating. Such an optionally partial coating can also be present, for example, in the interior of agglomerates of primary particles (i) and primary particles (ii), ie in pores.
In einer Ausführungsform der vorliegenden Erfindung liegen Kohlenstoff (iii) und Agglomerate von Primärpartikeln (i) und Primärpartikeln (ii) in diskreten Partikeln, die einander punktförmig oder gar nicht kontaktieren, nebeneinander vor. In einer Ausführungsform der vorliegenden Erfindung liegt Kohlenstoff (iii) teilweise als Beschichtung von Agglomeraten von Primärpartikeln (i) und Primärpartikeln (ii) als auch in Form separater Partikel vor. In one embodiment of the present invention, carbon (iii) and agglomerates of primary particles (i) and primary particles (ii) are present next to each other in discrete particles which contact each other punctiformly or not at all. In one embodiment of the present invention, carbon (iii) is present partially as a coating of agglomerates of primary particles (i) and primary particles (ii) as well as in the form of separate particles.
Die vorstehend beschriebene Morphologie von Kohlenstoff (iii) und von Agglomeraten von Pri- märpartikeln (i) und Primärpartikeln (ii) lässt sich beispielsweise durch Lichtmikroskopie, Transmissionselektronenmikroskopie (TEM) oder Rasterelektronenmikroskopie (SEM) oder SEM an Schnittaufnahmen nachweisen, außerdem beispielsweise röntgenographisch am Beugungsbild. In einer Ausführungsform der vorliegenden Erfindung liegen Agglomerate von Primärpartikeln (i) und Primärpartikeln (ii) in Form von Partikeln vor, die einen mittleren Partikeldurchmesser im Bereich von 1 bis 150 μηη (D50) aufweisen. Bevorzugt sind mittlere Partikeldurchmesser (D50) der Agglomerate im Bereich von 1 bis 50 μηη, besonders bevorzugt im Bereich von 1 bis 30 μηη, beispielsweise bestimmbar durch Laserbeugung. The above-described morphology of carbon (iii) and of agglomerates of primary particles (i) and primary particles (ii) can be demonstrated, for example, by means of light microscopy, transmission electron microscopy (TEM) or scanning electron microscopy (SEM) or SEM on sectional images, and also, for example, by X-ray diffraction , In one embodiment of the present invention, agglomerates of primary particles (i) and primary particles (ii) are in the form of particles having an average particle diameter in the range from 1 to 150 μm (D50). Preference is given to mean particle diameters (D50) of the agglomerates in the range from 1 to 50 μm, particularly preferably in the range from 1 to 30 μm, for example determinable by laser diffraction.
In einer Ausführungsform der vorliegenden Erfindung liegen Agglomerate von Primärpartikeln (i) und Primärpartikeln (ii) in Form von Partikeln vor, die einen mittleren Porendurchmesser im Bereich von 0,05 μηη bis 2 μηη aufweisen und die in Agglomeraten vorliegen können. Der mittlere Porendurchmesser lässt sich beispielsweise durch Quecksilberporosimetrie bestimmen, bei- spielsweise nach DIN 66133. In einer Ausführungsform der vorliegenden Erfindung liegen Agglomerate von Primärpartikeln (i) und Primärpartikeln (ii) in Form von Partikeln vor, die einen mittleren Porendurchmesser im Bereich von 0,05 μηη bis 2 μηη aufweisen und einen mono- oder multimodale Verlauf der Intrusi- onsvolumina im Bereich 100 bis 0,001 μηη zeigen und dabei vorzugsweise ein ausgeprägtes Maximum im Bereich zwischen 10 μηη und 1 μηη aufweisen, bevorzugt zwei ausgeprägte Maxi- ma, je eins zwischen 10 und 1 sowie zwischen 1 und 0,1 μηη. In one embodiment of the present invention, agglomerates of primary particles (i) and primary particles (ii) are present in the form of particles which have a mean pore diameter in the range of 0.05 μm to 2 μm and which can be present in agglomerates. The mean pore diameter can be determined, for example, by mercury porosimetry, for example according to DIN 66133. In one embodiment of the present invention, agglomerates of primary particles (i) and primary particles (ii) are present in the form of particles having an average pore diameter in the range from 0.05 μm to 2 μm and a mono- or multimodal course of the intrusion volumes in the range from 100 to 0.001 μm and preferably have a pronounced maximum in the range between 10 μm and 1 μm, preferably two pronounced maxima, one each between 10 and 1 and between 1 and 0.1 μm.
Bei Kohlenstoff (iii) handelt es sich beispielsweise um Ruß, Graphit, Graphen, Kohlenstoff- Nanoröhren, expandierte Graphite, interkalierte Graphite oder Aktivkohle. Carbon (iii) is, for example, carbon black, graphite, graphene, carbon nanotubes, expanded graphites, intercalated graphites or activated carbon.
In einer Ausführungsform der vorliegenden Erfindung handelt es sich bei Kohlenstoff (iii) um Ruß. Ruß kann beispielsweise gewählt werden aus Lampenruß, Ofenruß, Flammenruß, Ther- malruß, Acetylenruß, Industrieruß und Furnace Ruß. Ruß kann Verunreinigungen enthalten, beispielsweise Kohlenwasserstoffe, insbesondere aromatische Kohlenwasserstoffe, oder Sau- erstoff-haltige Verbindungen bzw. Sauerstoff-haltige Gruppen wie beispielsweise OH-Gruppen, Epoxidgruppen, Carbonyl-Gruppen und/oder Carboxyl-Gruppen. Weiterhin sind Schwefel- oder Eisen-haltige Verunreinigungen in Ruß möglich. In one embodiment of the present invention, carbon (iii) is carbon black. Carbon black may, for example, be selected from lampblack, furnace black, flame black, thermal black, acetylene black, carbon black and furnace carbon black. Carbon black may contain impurities, for example hydrocarbons, in particular aromatic hydrocarbons, or oxygen-containing compounds or oxygen-containing groups, for example OH groups, epoxide groups, carbonyl groups and / or carboxyl groups. Furthermore, sulfur or iron-containing impurities in carbon black are possible.
In einer Variante handelt es sich bei Kohlenstoff (iii) um partiell oxidierten Ruß. Partiell oxidierter Ruß, auch als aktivierter Ruß bezeichnet, enthält Sauerstoff-haltige Gruppen wie beispielsweise OH-Gruppen, Epoxidgruppen, Carbonyl-Gruppen und/oder Carboxyl-Gruppen. In a variant, carbon (iii) is partially oxidized carbon black. Partially oxidized carbon black, also referred to as activated carbon black, contains oxygen-containing groups such as, for example, OH groups, epoxide groups, carbonyl groups and / or carboxyl groups.
In einer Ausführungsform der vorliegenden Erfindung handelt es sich Kohlenstoff (iii) um Koh- lenstoff-Nanoröhren. Kohlenstoff-Nanoröhren (Kohlenstoffnanoröhren, kurz CNT oder englisch carbon nanotubes), beispielsweise einwandige Kohlenstoffnanoröhren (englisch single-walled carbon nanotubes, SW CNT) und bevorzugt mehrwandige Kohlenstoffnanoröhren (englisch multi-walled carbon nanotubes, MW CNT), sind an sich bekannt. Ein Verfahren zu ihrer Herstellung und einige Eigenschaften werden beispielsweise von A. Jess et al. in Chemie Ingenieur Techni 2006, 78, 94 - 100 beschrieben. In one embodiment of the present invention, carbon (iii) is carbon nanotubes. Carbon nanotubes (carbon nanotubes, short CNT or English carbon nanotubes), for example single-walled carbon nanotubes (SW CNT) and preferably multi-walled carbon nanotubes (MW CNT), are known per se. A process for their preparation and some properties are described, for example, by A. Jess et al. in Chemie Ingenieur Techni 2006, 78, 94 - 100.
In einer Ausführungsform der vorliegenden Erfindung haben Kohlenstoffnanoröhren einen Durchmesser im Bereich von 0,4 bis 50 nm, bevorzugt 1 bis 25 nm. In one embodiment of the present invention, carbon nanotubes have a diameter in the range of 0.4 to 50 nm, preferably 1 to 25 nm.
In einer Ausführungsform der vorliegenden Erfindung haben Kohlenstoffnanoröhren eine Länge im Bereich von 10 nm bis 1 mm, bevorzugt 100 nm bis 500 nm. In one embodiment of the present invention, carbon nanotubes have a length in the range of 10 nm to 1 mm, preferably 100 nm to 500 nm.
Kohlenstoff-Nanoröhren kann man nach an sich bekannten Verfahren herstellen. Beispielsweise kann man eine flüchtige Kohlenstoff-haltige Verbindung wie beispielsweise Methan oder Kohlenmonoxid, Acetylen oder Ethylen, oder ein Gemisch von flüchtigen Kohlenstoff-haltigen Verbindungen wie beispielsweise Synthesegas in Gegenwart von einem oder mehreren Reduktionsmitteln wie beispielsweise Wasserstoff und/oder einem weiteren Gas wie beispielsweise Stickstoff zersetzen. Ein anderes geeignetes Gasgemisch ist eine Mischung von Kohlenmono- xid mit Ethylen. Geeignete Temperaturen zur Zersetzung liegen beispielsweise im Bereich von 400 bis 1000°C, bevorzugt 500 bis 800°C. Geeignete Druckbedingungen für die Zersetzung sind beispielsweise im Bereich von Normaldruck bis 100 bar, bevorzugt bis 10 bar. Ein- oder mehrwandige Kohlenstoffnanorohren kann man beispielsweise durch Zersetzung von Kohlenstoff-haltigen Verbindungen im Lichtbogen erhalten, und zwar in Anwesenheit bzw. Abwesenheit eines Zersetzungskatalysators. Carbon nanotubes can be prepared by methods known per se. For example, one can use a volatile carbon-containing compound such as methane or carbon monoxide, acetylene or ethylene, or a mixture of volatile carbon-containing compounds such as synthesis gas in the presence of one or more reducing agents such as hydrogen and / or another gas such as nitrogen decompose. Another suitable gas mixture is a mixture of carbon mono- xid with ethylene. Suitable decomposition temperatures are, for example, in the range from 400 to 1000.degree. C., preferably from 500 to 800.degree. Suitable pressure conditions for the decomposition are, for example, in the range of atmospheric pressure to 100 bar, preferably up to 10 bar. Single- or multi-walled carbon nanotubes can be obtained, for example, by decomposition of carbon-containing compounds in the arc, in the presence or absence of a decomposition catalyst.
In einer Ausführungsform führt man die Zersetzung von flüchtiger Kohlenstoff-haltiger Verbin- dung bzw. Kohlenstoff-haltigen Verbindungen in Gegenwart eines Zersetzungskatalysators durch, beispielsweise Fe, Co oder bevorzugt Ni. In one embodiment, the decomposition of volatile carbon-containing compound or carbon-containing compounds in the presence of a decomposition catalyst, for example Fe, Co or preferably Ni.
Unter Graphen wird im Rahmen der vorliegenden Erfindung fast ideal oder ideal zweidimensionale hexagonale Kohlenstoffkristalle verstanden, die analog zu einzelnen Graphitschichten auf- gebaut sind. Sie können eine C-Atom-Schicht dick sein oder nur wenige, beispielsweise 2 bis 5 C-Atom-Schichten. Man kann Graphen durch Exfoliation oder durch Delaminierung von Graphit herstellen. In the context of the present invention, graphene is understood as meaning almost ideal or ideally two-dimensional hexagonal carbon crystals, which are constructed analogously to individual graphite layers. They can be one C-atom layer thick or only a few, for example 2 to 5 C-atom layers. Graphene can be prepared by exfoliation or by delamination of graphite.
Unter interkalierten Graphiten werden im Rahmen der vorliegenden Erfindung nicht vollständig delaminierte Graphite verstanden, die andere Atome, Ionen oder Verbindungen zwischen den hexagonalen C-Atom-Schichten eingelagert enthalten. Eingelagert können beispielsweise Alkalimetallionen sein, SO3, Nitrat oder Acetat. Die Herstellung interkalierter Graphite (auch: Blähgraphite) sind bekannt, siehe beispielsweise Rüdorff, Z. anorg. Allg. Chem. 1938, 238(1 ), 1. Interkalierte Graphite sind z.B. durch thermische Expansion von Graphit darstellbar. In the context of the present invention, intercalated graphites are understood to mean not completely delaminated graphites which contain other atoms, ions or compounds intercalated between the hexagonal C atom layers. For example, alkali metal ions, SO 3, nitrate or acetate can be incorporated. The production of intercalated graphites (also: expandable graphites) are known, see for example Rüdorff, Z. anorg. Gen. Chem. 1938, 238 (1), 1. Intercalated graphites are e.g. represented by thermal expansion of graphite.
Expandierte Graphite kann man beispielsweise durch Expansion interkalierter Graphite erhalten, siehe z.B. McAllister et al. Chem. Mater. 2007, 19, 4396-4404. Expanded graphites can be obtained, for example, by expansion of intercalated graphites, see e.g. McAllister et al. Chem. Mater. 2007, 19, 4396-4404.
In einer Ausführungsform der vorliegenden Erfindung handelt es sich bei erfindungsgemäßen Elektrodenmaterialien um solche, die man nach dem vorstehend beschriebenen erfindungsgemäßen Verfahren hergestellt hat. In one embodiment of the present invention, the electrode materials according to the invention are those which have been prepared by the method according to the invention described above.
In einer Ausführungsform der vorliegenden Erfindung enthält erfindungsgemäßes Elektrodenmaterial zusätzlich mindestens ein Bindemittel (iv), beispielsweise ein polymeres Bindemittel. In one embodiment of the present invention, electrode material according to the invention additionally contains at least one binder (iv), for example a polymeric binder.
Geeignete Bindemittel (iv) sind vorzugsweise gewählt aus organischen (Co)polymeren. Geeignete (Co)polymere, also Homopolymere oder Copolymere, kann man beispielsweise wählen aus durch anionische, katalytische oder radikalische (Co)polymerisation erhältlichen Suitable binders (iv) are preferably selected from organic (co) polymers. Suitable (co) polymers, ie homopolymers or copolymers, can be selected, for example, from anionic, catalytic or free-radical (co) polymerization
(Co)polymeren, insbesondere aus Polyethylen, Polyacrylnitril, Polybutadien, Polystyrol, und Copolymeren von mindestens zwei Comonomeren, gewählt aus Ethylen, Propylen, Styrol,(Co) polymers, in particular of polyethylene, polyacrylonitrile, polybutadiene, polystyrene, and copolymers of at least two comonomers selected from ethylene, propylene, styrene,
(Meth)acrylnitril und 1 ,3-Butadien. Außerdem ist Polypropylen geeignet. Weiterhin sind Polyiso- pren und Polyacrylate geeignet. Besonders bevorzugt ist Polyacrylnitril. Unter Polyacrylnitril werden im Rahmen der vorliegenden Erfindung nicht nur Polyacrylnitril- Homopolymere verstanden, sondern auch Copolymere von Acrylnitril mit 1 ,3-Butadien oder Styrol. Bevorzugt sind Polyacrylnitril-Homopolymere. (Meth) acrylonitrile and 1, 3-butadiene. In addition, polypropylene is suitable. Furthermore, polyisoprene and polyacrylates are suitable. Particularly preferred is polyacrylonitrile. In the context of the present invention, polyacrylonitrile is understood to mean not only polyacrylonitrile homopolymers, but also copolymers of acrylonitrile with 1,3-butadiene or styrene. Preference is given to polyacrylonitrile homopolymers.
Im Rahmen der vorliegenden Erfindung wird unter Polyethylen nicht nur Homo-Polyethylen verstanden, sondern auch Copolymere des Ethylens, die mindestens 50 mol-% Ethylen einpolyme- risiert enthalten und bis zu 50 mol-% von mindestens einem weiteren Comonomer, beispielsweise α-Olefine wie Propylen, Butylen (1 -Buten), 1 -Hexen, 1 -Octen, 1 -Decen, 1 -Dodecen, 1 - Penten, weiterhin Isobuten, Vinylaromaten wie beispielsweise Styrol, weiterhin In the context of the present invention, polyethylene is understood to mean not only homo-polyethylene, but also copolymers of ethylene which contain at least 50 mol% of ethylene and up to 50 mol% of at least one further comonomer, for example α-olefins such as Propylene, butylene (1-butene), 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-pentene, furthermore isobutene, vinylaromatics such as styrene, for example
(Meth)acrylsäure, Vinylacetat, Vinylpropionat, Ci-Cio-Alkylester der (Meth)acrylsäure, insbesondere Methylacrylat, Methylmethacrylat, Ethylacrylat, Ethylmethacrylat, n-Butylacrylat, 2- Ethylhexylacrylat, n-Butylmethacrylat, 2-Ethylhexylmethacrylat, weiterhin Maleinsäure, Maleinsäureanhydrid und Itaconsäureanhydrid. Bei Polyethylen kann es sich um HDPE oder um LDPE handeln. (Meth) acrylic acid, vinyl acetate, vinyl propionate, Ci-Cio-alkyl esters of (meth) acrylic acid, in particular methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, 2-ethylhexyl acrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, further maleic acid, maleic anhydride and itaconic. Polyethylene may be HDPE or LDPE.
Im Rahmen der vorliegenden Erfindung wird unter Polypropylen nicht nur Homo-Polypropylen verstanden, sondern auch Copolymere des Propylens, die mindestens 50 mol-% Propylen ein- polymerisiert enthalten und bis zu 50 mol-% von mindestens einem weiteren Comonomer, beispielsweise Ethylen und α-Olefine wie Butylen, 1 -Hexen, 1 -Octen, 1 -Decen, 1 -Dodecen und 1 - Penten. Bei Polypropylen handelt es sich vorzugsweise um isotaktisches oder um im Wesentlichen isotaktisches Polypropylen. In the context of the present invention, polypropylene is understood to mean not only homo-polypropylene but also copolymers of propylene which contain at least 50 mol% of propylene polymerized and up to 50 mol% of at least one further comonomer, for example ethylene and α-propylene. Olefins such as butylene, 1-hexene, 1-octene, 1-decene, 1-dodecene and 1-pentene. Polypropylene is preferably isotactic or substantially isotactic polypropylene.
Im Rahmen der vorliegenden Erfindung werden unter Polystyrol nicht nur Homopolymere des Styrols verstanden, sondern auch Copolymere mit Acrylnitril, 1 ,3-Butadien, (Meth)acrylsäure, Ci-Cio-Alkylester der (Meth)acrylsäure, Divinylbenzol, insbesondere 1 ,3-Divinylbenzol, 1 ,2- Diphenylethylen und a-Methylstyrol. In the context of the present invention, polystyrene is understood to mean not only homopolymers of styrene, but also copolymers with acrylonitrile, 1,3-butadiene, (meth) acrylic acid, C 1 -C 10 -alkyl esters of (meth) acrylic acid, divinylbenzene, in particular 1, 3. Divinylbenzene, 1, 2-diphenylethylene and a-methylstyrene.
Ein anderes bevorzugtes Bindemittel (iv) ist Polybutadien. Andere geeignete Bindemittel (iv) sind gewählt aus Polyethylenoxid (PEO), Cellulose, Car- boxymethylcellulose, Polyimiden und Polyvinylalkohol. Another preferred binder (iv) is polybutadiene. Other suitable binders (iv) are selected from polyethylene oxide (PEO), cellulose, carboxymethylcellulose, polyimides and polyvinyl alcohol.
In einer Ausführungsform der vorliegenden Erfindung wählt man Bindemittel (iv) aus solchen (Co)polymeren, die ein mittleres Molekulargewicht Mw im Bereich von 50.000 bis 1 .000.000 g/mol, bevorzugt bis 500.000 g/mol aufweisen. In one embodiment of the present invention, binders (iv) are selected from those (co) polymers which have an average molecular weight M w in the range from 50,000 to 1,000,000 g / mol, preferably up to 500,000 g / mol.
Bei Bindemitteln (iv) kann es sich um vernetzte oder unvernetzte (Co)polymere handeln. Binders (iv) may be crosslinked or uncrosslinked (co) polymers.
In einer besonders bevorzugten Ausführungsform der vorliegenden Erfindung wählt man Bin- demittel (iv) aus halogenierten (Co)polymeren, insbesondere aus fluorierten (Co)polymeren. Dabei werden unter halogenierten bzw. fluorierten (Co)polymeren solche (Co)polymere verstanden, die mindestens ein (Co)monomer einpolymerisiert enthalten, das mindestens ein Ha- logenatom bzw. mindestens ein Fluoratom pro Molekül aufweist, bevorzugt mindestens zwei Halogenatome bzw. mindestens zwei Fluoratome pro Molekül. In a particularly preferred embodiment of the present invention, binder (iv) is selected from halogenated (co) polymers, in particular from fluorinated (co) polymers. Halogenated or fluorinated (co) polymers are understood as meaning those (co) polymers which contain at least one (co) monomer in copolymerized form, which contains at least one or at least one fluorine atom per molecule, preferably at least two halogen atoms or at least two fluorine atoms per molecule.
Beispiele sind Polyvinylchlorid, Polyvinylidenchlorid, Polytetrafluorethylen, Polyvinylidenfluorid (PVdF), Tetrafluoroethylen-Hexafluorpropylen-Copolymere, Vinylidenfluorid-Hexafluorpropylen- Copolymere (PVdF-HFP), Vinylidenfluorid-Tetrafluorethylen-Copolymere, Perfluoralkylvi- nylether-Copolymere, Ethylen-Tetrafluorethylen-Copolymere, Vinylidenfluorid- Chlortrifluorethylen-Copolymere und Ethylen-Chlorfluorethylen-Copolymere. Geeignete Bindemittel (iv) sind insbesondere Polyvinylalkohol und halogenierte (Co)polymere, beispielsweise Polyvinylchlorid oder Polyvinylidenchlorid, insbesondere fluorierte (Co)polymere wie Polyvinylfluorid und insbesondere Polyvinylidenfluorid und Polytetrafluorethylen. Examples are polyvinyl chloride, polyvinylidene chloride, polytetrafluoroethylene, polyvinylidene fluoride (PVdF), tetrafluoroethylene-hexafluoropropylene copolymers, vinylidene fluoride-hexafluoropropylene copolymers (PVdF-HFP), vinylidene fluoride-tetrafluoroethylene copolymers, perfluoroalkylvinyl ether copolymers, ethylene-tetrafluoroethylene copolymers, vinylidene fluoride copolymers. Chlorotrifluoroethylene copolymers and ethylene-chlorofluoroethylene copolymers. Suitable binders (iv) are in particular polyvinyl alcohol and halogenated (co) polymers, for example polyvinyl chloride or polyvinylidene chloride, in particular fluorinated (co) polymers such as polyvinyl fluoride and in particular polyvinylidene fluoride and polytetrafluoroethylene.
In einer Ausführungsform der vorliegenden Erfindung enthält erfindungsgemäßes Elektroden- material: In one embodiment of the present invention, electrode material according to the invention contains:
insgesamt im Bereich von 60 bis 98 Gew.-%, bevorzugt 70 bis 96 Gew.-% Agglomerate von Primärpartikeln (i) und Primärpartikeln (ii), in total in the range of 60 to 98% by weight, preferably 70 to 96% by weight, of agglomerates of primary particles (i) and primary particles (ii),
im Bereich von 1 bis 25 Gew.-% bevorzugt 2 bis 20 Gew.-% Kohlenstoff (iii), in the range of 1 to 25% by weight, preferably 2 to 20% by weight, of carbon (iii),
im Bereich von 1 bis 20 Gew.-%, bevorzugt 2 bis 15 Gew.-% Bindemittel (iv). in the range of 1 to 20 wt .-%, preferably 2 to 15 wt .-% binder (iv).
Erfindungsgemäße Elektrodenmaterialien lassen sich gut zur Herstellung von elektrochemischen Zellen verwenden. Beispielsweise lassen sie sich zu Pasten mit guten rheologischen Eigenschaften verarbeiten. Ein weiterer Gegenstand der vorliegenden Erfindung sind elektrochemische Zellen, hergestellt unter Verwendung von mindestens einer erfindungsgemäßen Elektrode. Ein weiterer Gegenstand der vorliegenden Erfindung sind elektrochemische Zellen, enthaltend mindestens eine erfindungsgemäße Elektrode. Ein weiterer Aspekt der vorliegenden Erfindung ist eine Elektrode, enthaltend Agglomerate von Primärpartikeln (i) und Primärpartikeln (ii), Kohlenstoff (iii) und mindestens ein Bindemittel (iv). Inventive electrode materials can be used well for the production of electrochemical cells. For example, they can be processed into pastes with good rheological properties. Another object of the present invention are electrochemical cells prepared using at least one electrode according to the invention. Another object of the present invention are electrochemical cells containing at least one electrode according to the invention. Another aspect of the present invention is an electrode containing agglomerates of primary particles (i) and primary particles (ii), carbon (iii) and at least one binder (iv).
Agglomerate von Primärpartikeln (i) und Primärpartikeln (ii), Kohlenstoff (iii) und Bindemittel (iv) sind vorstehend beschrieben. Agglomerates of primary particles (i) and primary particles (ii), carbon (iii) and binder (iv) are described above.
Die Geometrie von erfindungsgemäßen Elektroden kann man in weiten Grenzen wählen. Bevorzugt ist es, erfindungsgemäße Elektroden in dünnen Filmen auszugestalten, beispielsweise in Filmen mit einer Dicke im Bereich von 10 μηη bis 250 μηη, bevorzugt 20 bis 130 μηη. The geometry of electrodes according to the invention can be chosen within wide limits. It is preferred to design electrodes according to the invention in thin films, for example in films with a thickness in the range from 10 μm to 250 μm, preferably from 20 to 130 μm.
In einer Ausführungsform der vorliegenden Erfindung umfassen erfindungsgemäße Elektroden eine Folie, beispielsweise eine Metallfolie, insbesondere eine Aluminiumfolie, oder eine Poly- merfolie, beispielsweise eine Polyesterfolie, die unbehandelt oder silikonisiert sein kann. Die Folie ist ein- oder beidseitig mit erfindungsgemäßem Elektrodenmaterial beschichtet. In one embodiment of the present invention, electrodes according to the invention comprise a foil, for example a metal foil, in particular an aluminum foil, or a polythene foil. merfolie, for example, a polyester film, which may be untreated or siliconized. The film is coated on one or both sides with inventive electrode material.
Ein weiterer Aspekt der vorliegenden Erfindung ist die Verwendung von erfindungsgemäßen Elektrodenmaterialien zur Herstellung von Elektroden von Lithium-Ionen-Batterien. Ein weiterer Aspekt der vorliegenden Erfindung ist ein Verfahren zur Herstellung von Elektroden unter Verwendung von erfindungsgemäßen Elektrodenmaterialien. Another aspect of the present invention is the use of electrode materials according to the invention for the production of electrodes of lithium-ion batteries. Another aspect of the present invention is a method of making electrodes using electrode materials of the invention.
Erfindungsgemäße Elektroden dienen in erfindungsgemäßen elektrochemischen Zellen definiti- onsgemäß als Kathoden. Erfindungsgemäße elektrochemische Zellen enthalten eine Gegenelektrode, die im Rahmen der vorliegenden Erfindung als Anode definiert wird und die beispielsweise eine Kohlenstoff-Anode, insbesondere eine Graphit-Anode, eine Lithium-Anode, eine Silizium-Anode oder eine Lithium-Titanat-Anode sein kann. Bei erfindungsgemäßen elektrochemischen Zellen kann es sich beispielsweise um Batterien oder um Akkumulatoren handeln. Electrochemical cells according to the invention definitely serve as cathodes in electrochemical cells according to the invention. Electrochemical cells according to the invention contain a counterelectrode which is defined as an anode in the context of the present invention and which can be, for example, a carbon anode, in particular a graphite anode, a lithium anode, a silicon anode or a lithium titanate anode. Electrochemical cells according to the invention may be, for example, batteries or accumulators.
Erfindungsgemäße elektrochemische Zellen können neben Anode und erfindungsgemäßer Elektrode weitere Bestandteile umfassen, beispielsweise Leitsalz, nicht-wässriges Lösungsmit- tel, Separator, Stromableiter, beispielsweise aus einem Metall oder einer Legierung, weiterhin Kabelverbindungen und Gehäuse. Electrochemical cells according to the invention can comprise, in addition to the anode and the electrode according to the invention, further constituents, for example conductive salt, nonaqueous solvent, separator, current conductor, for example of a metal or an alloy, furthermore cable connections and housing.
In einer Ausführungsform der vorliegenden Erfindung enthalten erfindungsgemäße elektrische Zellen mindestens ein nicht-wässriges Lösungsmittel, das bei Zimmertemperatur flüssig oder fest sein kann, bevorzugt gewählt aus Polymeren, cyclischen oder nicht-cyclischen Ethern, cyclischen und nicht-cyclischen Acetalen und cyclischen oder nicht cyclischen organischen Carbo- naten. In one embodiment of the present invention, electrical cells according to the invention contain at least one non-aqueous solvent, which may be liquid or solid at room temperature, preferably selected from polymers, cyclic or non-cyclic ethers, cyclic and non-cyclic acetals and cyclic or non-cyclic organic Carbonates.
Beispiele für geeignete Polymere sind insbesondere Polyalkylenglykole, bevorzugt P0IV-C1-C4- alkylenglykole und insbesondere Polyethylenglykole. Dabei können Polyethylenglykole bis zu 20 mol-% ein oder mehrere Ci-C4-Alkylenglykole einpolymerisiert enthalten. Vorzugsweise handelt es sich bei Polyalkylenglykolen um zweifach mit Methyl oder Ethyl verkappte Polyalkylenglykole. Das Molekulargewicht Mw von geeigneten Polyalkylenglykolen und insbesondere von geeigneten Polyethylenglykolen kann mindestens 400 g/mol betragen. Examples of suitable polymers are in particular polyalkylene glycols, preferably P0IV-C1-C4-alkylene glycols and in particular polyethylene glycols. Polyethylene glycols may contain up to 20 mol% of one or more C 1 -C 4 -alkylene glycols in copolymerized form. Preferably, polyalkylene glycols are polyalkylene glycols double capped with methyl or ethyl. The molecular weight M w of suitable polyalkylene glycols and especially of suitable polyethylene glycols may be at least 400 g / mol.
Das Molekulargewicht Mw von geeigneten Polyalkylenglykolen und insbesondere von geeigneten Polyethylenglykolen kann bis zu 5.000.000 g/mol betragen, bevorzugt bis zu 2.000.000 g/mol betragen Beispiele für geeignete nicht-cyclische Ether sind beispielsweise Diisopropylether, Di-n- Butylether, 1 ,2-Dimethoxyethan, 1 ,2-Diethoxyethan, bevorzugt ist 1 ,2-Dimethoxyethan. The molecular weight M w of suitable polyalkylene glycols and in particular of suitable polyethylene glycols may be up to 5,000,000 g / mol, preferably up to 2,000,000 g / mol Examples of suitable non-cyclic ethers are, for example, diisopropyl ether, di-n-butyl ether, 1, 2-dimethoxyethane, 1, 2-diethoxyethane, preference is 1, 2-dimethoxyethane.
Beispiele für geeignete cyclische Ether sind Tetrahydrofuran und 1 ,4-Dioxan. Examples of suitable cyclic ethers are tetrahydrofuran and 1,4-dioxane.
Beispiele für geeignete nicht-cyclische Acetale sind beispielsweise Dimethoxymethan, Diet- hoxymethan, 1 ,1 -Dimethoxyethan und 1 ,1 -Diethoxyethan. Examples of suitable non-cyclic acetals are, for example, dimethoxymethane, diethoxymethane, 1,1-dimethoxyethane and 1,1-diethoxyethane.
Beispiele für geeignete cyclische Acetale sind 1 ,3-Dioxan und insbesondere 1 ,3-Dioxolan. Beispiele für geeignete nicht-cyclische organische Carbonate sind Dimethylcarbonat, Ethylme- thylcarbonat und Diethylcarbonat. Examples of suitable cyclic acetals are 1, 3-dioxane and in particular 1, 3-dioxolane. Examples of suitable non-cyclic organic carbonates are dimethyl carbonate, ethyl methyl carbonate and diethyl carbonate.
Beispiele für geeignete cyclische organische Carbonate sind Verbindungen der allgemeinen Formeln (II) und (III) Examples of suitable cyclic organic carbonates are compounds of the general formulas (II) and (III)
bei denen R3, R4 und R5 gleich oder verschieden sein können und gewählt aus Wasserstoff und Ci-C4-Alkyl, beispielsweise Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl, wobei vorzugsweise R4 und R5 nicht beide tert.-Butyl sind. in which R 3 , R 4 and R 5 may be identical or different and selected from hydrogen and C 1 -C 4 -alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec. Butyl and tert-butyl, preferably R 4 and R 5 are not both tert-butyl.
In besonders bevorzugten Ausführungsformen ist R3 Methyl und R4 und R5 sind jeweils Wasserstoff, oder R5, R3 und R4 sind jeweils gleich Wasserstoff. Ein anderes bevorzugtes cyclisches organisches Carbonat ist Vinylencarbonat, Formel (IV). In particularly preferred embodiments, R 3 is methyl and R 4 and R 5 are each hydrogen or R 5 , R 3 and R 4 are each hydrogen. Another preferred cyclic organic carbonate is vinylene carbonate, formula (IV).
Vorzugsweise setzt man das oder die Lösungsmittel im so genannten wasserfreien Zustand ein, d.h. mit einem Wassergehalt im Bereich von 1 ppm bis 0,1 Gew.-%, bestimmbar beispielsweise durch Karl-Fischer-Titration. Erfindungsgemäße elektrochemische Zellen enthalten weiterhin mindestens ein Leitsalz. Geeignete Leitsalze sind insbesondere Lithiumsalze. Beispiele für geeignete Lithiumsalze sind LiPF6, LiBF4, UCIO4, LiAsFe, L1CF3SO3, LiC(CnF2n+iS02)3, Lithiumimide wie LiN(CnF2n+iS02)2, wobei n eine ganze Zahl im Bereich von 1 bis 20 ist, LiN(S02F)2, Li2SiF6, LiSbF6, LiAICU, und Salze der allgemeinen Formel (CnF2n+iS02)mYLi, wobei m wie folgt definiert ist: The solvent (s) are preferably used in the so-called anhydrous state, ie with a water content in the range from 1 ppm to 0.1% by weight, determinable for example by Karl Fischer titration. Inventive electrochemical cells also contain at least one conductive salt. Suitable conductive salts are in particular lithium salts. Examples of suitable lithium salts are LiPF 6, LiBF 4, UCIO4, LiAsFe, L1CF3SO3, LiC (CnF 2n + IS02) 3, lithium imides such as LiN (CnF 2 n + IS02) 2, where n is an integer ranging from 1 to 20; LiN (SO 2 F) 2, Li 2 SiF 6, LiSbF 6, LiAICU, and salts of the general formula (C n F 2n + i SO 2) mYLi, where m is defined as follows:
m = 1 , wenn Y gewählt wird aus Sauerstoff und Schwefel, m = 1, when Y is selected from oxygen and sulfur,
m = 2, wenn Y gewählt wird aus Stickstoff und Phosphor, und m = 2 when Y is selected from nitrogen and phosphorus, and
m = 3, wenn Y gewählt wird aus Kohlenstoff und Silizium. m = 3 when Y is selected from carbon and silicon.
Bevorzugte Leitsalze sind gewählt aus LiC(CF3S02)3, LiN(CF3S02)2, LiPF6, LiBF4, Preferred conducting salts are selected from LiC (CF 3 SO 2 ) 3 , LiN (CF 3 SO 2 ) 2 , LiPF 6 , LiBF 4 ,
L1CIO4, und besonders bevorzugt sind LiPF6 und LiN(CFsS02)2. L1CIO4, and particularly preferred are LiPF6 and LiN (CFsSO2) 2.
In einer Ausführungsform der vorliegenden Erfindung enthalten erfindungsgemäße elektrochemische Zellen einen oder mehrere Separatoren, durch die die Elektroden mechanisch getrennt sind. Als Separatoren sind Polymerfilme, insbesondere poröse Polymerfilme, geeignet, die ge- genüber metallischem Lithium unreaktiv sind. Besonders geeignete Materialien für Separatoren sind Polyolefine, insbesondere filmförmiges poröses Polyethylen und filmförmiges poröses Polypropylen. In one embodiment of the present invention, electrochemical cells according to the invention contain one or more separators, by means of which the electrodes are mechanically separated. Suitable separators are polymer films, in particular porous polymer films, which are unreactive with respect to metallic lithium. Particularly suitable materials for separators are polyolefins, in particular film-shaped porous polyethylene and film-shaped porous polypropylene.
Separatoren aus Polyolefin, insbesondere aus Polyethylen oder Polypropylen, können eine Po- rosität im Bereich von 35 bis 45% haben. Geeignete Porendurchmesser liegen beispielsweise im Bereich von 30 bis 500 nm. Polyolefin separators, especially polyethylene or polypropylene, may have a porosity in the range of 35 to 45%. Suitable pore diameters are for example in the range from 30 to 500 nm.
In einer anderen Ausführungsform der vorliegenden Erfindung kann man Separatoren aus mit anorganischen Partikeln gefüllten PET-Vliesen wählen. Derartige Separatoren können eine Po- rosität im Bereich von 40 bis 55 % aufweisen. Geeignete Porendurchmesser liegen beispielsweise im Bereich von 80 bis 750 nm. In another embodiment of the present invention, separators may be selected from inorganic particle filled PET webs. Such separators may have a porosity in the range of 40 to 55%. Suitable pore diameters are for example in the range of 80 to 750 nm.
Erfindungsgemäße elektrochemische Zellen enthalten weiterhin ein Gehäuse, das beliebige Form haben kann, beispielsweise quaderförmig oder die Form einer zylindrischen Scheibe. In einer Variante wird als Gehäuse eine als Beutel ausgearbeitete Metallfolie eingesetzt. Electrochemical cells according to the invention furthermore contain a housing which can have any shape, for example cuboidal or the shape of a cylindrical disk. In one variant, a metal foil developed as a bag is used as the housing.
Erfindungsgemäße elektrochemische Zellen lassen sich miteinander kombinieren, beispielsweise in Reihenschaltung oder in Parallelschaltung. Reihenschaltung ist bevorzugt. Ein weiterer Gegenstand der vorliegenden Erfindung ist die Verwendung von erfindungsgemäßen elektrochemischen Zellen in Geräten, insbesondere in mobilen Geräten. Beispiele für mobile Geräte sind Fahrzeuge, beispielsweise Automobile, Zweiräder, Flugzeuge oder Wasserfahr- zeuge wie Boote oder Schiffe. Andere Beispiele für mobile Geräte sind solche, die man selber bewegt, beispielsweise Computer, insbesondere Laptops, Telefone oder elektrische Handwerkszeuge, beispielsweise aus dem Bereich des Bauens, insbesondere Bohrmaschinen, Ak- kubohrschrauber oder Akku-Tacker. Inventive electrochemical cells can be combined with each other, for example in series or in parallel. Series connection is preferred. Another object of the present invention is the use of electrochemical cells according to the invention in devices, in particular in mobile devices. Examples of mobile devices are vehicles, such as automobiles, two-wheeled vehicles, aircraft or watercraft. witnesses like boats or ships. Other examples of mobile devices are those that you move yourself, for example computers, especially laptops, telephones or electrical tools, for example in the field of construction, in particular drills, cordless screwdrivers or cordless tackers.
Ein weiterer Aspekt der vorliegenden Erfindung sind Lithium-Ionen-Batterien, enthaltend mindestens eine Elektrode, enthaltend mindestens ein erfindungsgemäßes Elektrodenmaterial. Ein weiterer Aspekt der vorliegenden Erfindung sind dementsprechend Lithium-Ionen-Batterien, enthaltend mindestens eine erfindungsgemäße Elektrode. Another aspect of the present invention are lithium-ion batteries, comprising at least one electrode, containing at least one electrode material according to the invention. Accordingly, another aspect of the present invention is lithium-ion batteries containing at least one electrode according to the invention.
Ein weiterer Aspekt der vorliegenden Erfindung ist die Verwendung von erfindungsgemäßen Lithium-Ionen-Batterien in Vorrichtungen, die Batterien mit einer hohen Spitzenleistung und damit einer schnellen Entladung erfordern. Beispiele für derartige Vorrichtungen sind Bohrmaschinen, Akkubohrschrauber oder Akku-Tacker oder Anlasser zum Kaltstart von Fahrzeugen, beispielsweise Automobilen oder Motorrädern. Erfindungsgemäße Lithium-Ionen-Batterien haben eine hohe Spitzenleistung. Bevorzugt übersteigt die Entladegeschwindigkeit wenigstens kurzzeitig 5C. Erfindungsgemäße Lithium-Ionen-Batterien lassen sich außerdem schnell entladen, wenn man es wünscht. Beispielsweise lassen sie sich bei nur geringfügig absinkender Kapazität innerhalb von 12 Minuten bei 5C, bevorzugt innerhalb von 6 Minuten bei 10C entladen. Another aspect of the present invention is the use of lithium-ion batteries of the invention in devices that require high-power, and thus fast-discharge, batteries. Examples of such devices are drills, cordless screwdrivers or cordless tackers or starters for cold starting of vehicles, such as automobiles or motorcycles. Lithium-ion batteries according to the invention have a high peak power. The discharge rate preferably exceeds 5C for at least a short time. Lithium-ion batteries according to the invention can also be discharged quickly, if desired. For example, they can be discharged at 10C within 12 minutes, preferably within 10 minutes, with only a slightly decreasing capacity.
Die Erfindung wird durch Arbeitsbeispiele erläutert. The invention will be explained by working examples.
Arbeitsbeispiele I. Herstellung eines Elektrodenmaterials Working Examples I. Preparation of an electrode material
1.1 Herstellung von erfindungsgemäßem Elektrodenmaterial EM.1  1.1 Production of Inventive Electrode Material EM.1
In Schritt (a.1 ) setzte man die folgenden Ausgangsmaterialien ein: In step (a.1), the following starting materials were used:
4,58 kg H3P03 (A.1 ) 4.58 kg H 3 P0 3 (A.1)
6,38 kg H3P04 (A.2) 6.38 kg H 3 P0 4 (A.2)
4,79 g LiOH ■ H20 (B.1 ) 4.79 g LiOH ■ H 2 O (B.1)
2,64 kg Laktose (C.1 ) 2.64 kg lactose (C.1)
3,12 kg Eisencitrat (D1 .1 ) 3.12 kg iron citrate (D1 .1)
8,83 kg α-FeOOH (D2.1 ) 8.83 kg of α-FeOOH (D2.1)
Zuerst wurden 108,8 kg vollentsalztes Wasser in einem 200-Liter-Doppelmantelrührgefäß mit Ankerrührer vorgelegt und auf 52°C aufgeheizt. Anschließend wurde das LiOH ■ H2O (B.1 ) darin gelöst und dann die Eisenverbindungen (D1 .1 ) und (D2.1 ) zugegeben. Danach wurden Phosphorverbindungen (A.1 ) und (A.2) zugegeben. Die Temperatur stieg auf 68°C. Danach gab man die Kohlenstoffquelle (C.1 ) zu. Man rührte bei 70°C über einen Zeitraum von vierzehn Stunden nach (pH-Wert: 4,5). Man erhielt eine gelbe Suspension. Trocknung First, 108.8 kg of demineralized water were placed in a 200 liter double-walled stirred vessel equipped with an anchor stirrer and heated to 52 ° C. Subsequently, the LiOH ■ H2O (B.1) was dissolved therein and then the iron compounds (D1 .1) and (D2.1) was added. Thereafter, phosphorus compounds (A.1) and (A.2) were added. The temperature rose to 68 ° C. Thereafter, the carbon source (C.1) was added. The mixture was stirred at 70 ° C. over a period of fourteen hours (pH value: 4.5). A yellow suspension was obtained. desiccation
Die Lösung aus Schritt (a.1 ) wurde in einem Sprühturm nach Programm unter Luft versprüht. Der Heißluftstrom hatte beim Eingang eine Temperatur von 305°C, beim Ausgang noch 121 °C. Der Trockner wurde mit 450 kg/h Trocknungsgas betrieben sowie 33 kg/h Düsengas (Zerstäu- bungsgas) mit einem Zerstäubungsdruck von 3,5 bar.  The solution from step (a.1) was sprayed in a spray tower by program under air. The hot air flow at the entrance had a temperature of 305 ° C, at the exit still 121 ° C. The dryer was operated with 450 kg / h of drying gas and 33 kg / h of nozzle gas (atomizing gas) with an atomization pressure of 3.5 bar.
Man erhielt ein gelbes gut rieselfähiges Pulver mit einer Restfeuchte von 8%. Es lag in Form von Partikeln vor, deren Durchmesser (D50) 22,6 μηη war. SEM-Bilder zeigten sphärische Agglomerate des gelben Pulvers, die im Inneren durch den organischen Bestandteil Laktose zu- sammengehalten wurden. A yellow free-flowing powder with a residual moisture content of 8% was obtained. It was in the form of particles whose diameter (D50) was 22.6 μηη. SEM images showed spherical agglomerates of yellow powder internally held by the organic component lactose.
Schritt (b.1 ) Step (b.1)
60 g des wie vorstehend beschrieben erhaltenen gelben Pulvers wurden in einem 2-I- Quarzdrehkugelofen unter IS -Atmosphäre thermisch behandelt. Die 2-l-Quarzdrehkugel drehte sich mit einer Geschwindigkeit von 10 Umdrehungen/min. Zunächst erhitzte man innerhalb von 60 Minuten auf 700°C. Dann kalzinierte man 60 Minuten bei 700°C. Danach ließ man auf Zimmertemperatur abkühlen. Man siebte (mesh 50 μηη) und erhielt ein erfindungsgemäßes Elektrodenmaterial EM.1 , welches schwarz aussah und pulverförmig anfiel. BET: 26 m2/g. 60 g of the yellow powder obtained as described above was thermally treated in a 2 liter quartz rotary kiln under an atmosphere of IS. The 2 liter quartz spin ball rotated at a speed of 10 rpm. First, it was heated to 700 ° C within 60 minutes. Then calcined for 60 minutes at 700 ° C. Then allowed to cool to room temperature. It was sieved (mesh 50 μηη) and received an inventive electrode material EM.1, which looked black and was obtained in powder form. BET: 26 m 2 / g.
Die Stampfdichte der Siebfraktion <32μηη betrug 0,73 g/ml. The tamped density of the sieve fraction <32μηη was 0.73 g / ml.
I.2 Herstellung von Vergleichs-Elektrodenmaterial V-EM.2 I.2 Preparation of comparative electrode material V-EM.2
In Schritt (a.2) setzte man die folgenden Ausgangsmaterialien ein:  In step (a.2), the following starting materials were used:
5,33 kg H3P03 (A.1 )5.33 kg H 3 P0 3 (A.1)
5,57 g LiOH ■ H20 (B.1 ) 5.57 g of LiOH ■ H 2 O (B.1)
4,1 1 kg Mannitol (C.2) 4.1 1 kg of mannitol (C.2)
I I , 42 kg α-FeOOH (D2.1 )  I, 42 kg α-FeOOH (D2.1)
Zuerst wurden 128 kg vollentsalztes Wasser in einem 200-Liter-Doppelmantelrührgefäß mit Ankerrührer vorgelegt und auf 57°C aufgeheizt. Anschließend wurde das LiOH ■ H2O (B.1 ) darin gelöst und dann die Eisenverbindung (D2.1 ) zugegeben. Danach wurden Phosphorverbindungen (A.1 ) und (A.2) zugegeben. Die Temperatur stieg auf 76°C. Danach gab man Kohlenstoff- quelle (C.2) zu. Man rührte bei 70°C über einen Zeitraum von vierzehn Stunden nach (pH-Wert: 4,6). Man erhielt eine gelbe Suspension. First, 128 kg of demineralized water were placed in a 200 liter double-walled stirred vessel equipped with an anchor stirrer and heated to 57 ° C. Subsequently, the LiOH ■ H2O (B.1) was dissolved therein and then the iron compound (D2.1) was added. Thereafter, phosphorus compounds (A.1) and (A.2) were added. The temperature rose to 76 ° C. Thereafter, carbon source (C.2) was added. The mixture was stirred at 70 ° C. over a period of fourteen hours (pH: 4.6). A yellow suspension was obtained.
Trocknung desiccation
Die Lösung aus Schritt (a.2) wurde in einem Sprühturm nach Programm unter Luft versprüht. Der Heißluftstrom hatte beim Eingang eine Temperatur von 305°C, beim Ausgang noch 121 °C. Der Trockner wurde mit 450 kg/h Trocknungsgas betrieben sowie 33 kg/h Düsengas (Zerstäubungsgas) mit einem Zerstäubungsdruck von 3,5 bar. Man erhielt ein gelbes gut rieselfähiges Pulver mit einer Restfeuchte von 8%. Es lag in Form von Partikeln vor, deren Durchmesser (D50) 18,3 μηη war. SEM-Bilder zeigten sphärische Agglomerate des gelben Pulvers, die im Inneren durch den organischen Bestandteil Mannitol zusammengehalten wurden. The solution from step (a.2) was sprayed in a spray tower by program under air. The hot air flow at the entrance had a temperature of 305 ° C, at the exit still 121 ° C. The dryer was operated with 450 kg / h of drying gas and 33 kg / h of nozzle gas (sputtering gas) with an atomization pressure of 3.5 bar. A yellow free-flowing powder with a residual moisture content of 8% was obtained. It was in the form of particles whose diameter (D50) was 18.3 μηη. SEM images showed spherical agglomerates of yellow powder held together by the organic component mannitol.
Schritt (b.2) Step (b.2)
60 g des wie vorstehend beschrieben erhaltenen gelben Pulvers wurden in einem 2-I- Quarzdrehkugelofen unter IS -Atmosphäre thermisch behandelt. Die 2-l-Quarzdrehkugel drehte sich mit einer Geschwindigkeit von 10 Umdrehungen/min. Zunächst erhitzte man innerhalb von 60 Minuten auf 700°C. Dann kalzinierte man 60 Minuten bei 700°C. Danach ließ man auf Zimmertemperatur abkühlen. Man siebte (mesh 50 μηη) und erhielt ein Elektrodenmaterial V-EM.2, welches schwarz aussah und pulverförmig anfiel. BET: 9,1 m2/g. Die Stampfdichte der Siebfraktion <32μηη betrug 1 ,01 g/ml. 60 g of the yellow powder obtained as described above was thermally treated in a 2 liter quartz rotary kiln under an atmosphere of IS. The 2 liter quartz spin ball rotated at a speed of 10 rpm. First, it was heated to 700 ° C within 60 minutes. Then calcined for 60 minutes at 700 ° C. Then allowed to cool to room temperature. It sieved (mesh 50 μηη) and received an electrode material V-EM.2, which looked black and was obtained in powder form. BET: 9.1 m 2 / g. The tamped density of the sieve fraction <32μηη was 1, 01 g / ml.
I.3 Herstellung von Vergleichs-Elektrodenmaterial V-EM.3 I.3 Preparation of comparative electrode material V-EM.3
In Schritt (a.3) setzte man die folgenden Ausgangsmaterialien ein: In step (a.3), the following starting materials were used:
5,66 kg H3P03 (A.1 )5.66 kg H 3 P0 3 (A.1)
5,92 g LiOH ■ H20 (B.1 ) 5.92 g of LiOH ■ H 2 O (B.1)
2,17 kg Laktose (C.1 ) 2.17 kg lactose (C.1)
2,00 kg Stärke (C.3) 2,00 kg starch (C.3)
12,14 kg α-FeOOH (D2.1 ) Zuerst wurden 136 kg vollentsalztes Wasser in einem 200-Liter-Doppelmantelrührgefäß mit12.14 kg α-FeOOH (D2.1) First, 136 kg of demineralized water were placed in a 200 liter double-walled stirred vessel
Ankerrührer vorgelegt und auf 53°C aufgeheizt. Anschließend wurde das LiOH ■ H2O (B.1 ) darin gelöst und dann die Eisenverbindung (D2.1 ) zugegeben. Danach wurden Phosphorverbindungen (A.1 ) und (A.2) zugegeben. Die Temperatur stieg auf 69°C. Danach gab man die Kohlenstoffquellen (C.1 ) und (C.3) zu. Man rührte bei 70°C über einen Zeitraum von vierzehn Stunden nach (pH-Wert: 4,6). Man erhielt eine gelbe Suspension. Anchor stirrer submitted and heated to 53 ° C. Subsequently, the LiOH ■ H2O (B.1) was dissolved therein and then the iron compound (D2.1) was added. Thereafter, phosphorus compounds (A.1) and (A.2) were added. The temperature rose to 69 ° C. Thereafter, the carbon sources (C.1) and (C.3) were added. The mixture was stirred at 70 ° C. over a period of fourteen hours (pH: 4.6). A yellow suspension was obtained.
Trocknung desiccation
Die Lösung aus Schritt (a.3) wurde in einem Sprühturm nach Programm unter Luft versprüht. Der Heißluftstrom hatte beim Eingang eine Temperatur von 305°C, beim Ausgang noch 121 °C. Der Trockner wurde mit 450 kg/h Trocknungsgas betrieben sowie 33 kg/h Düsengas (Zerstäubungsgas) mit einem Zerstäubungsdruck von 3,5 bar.  The solution from step (a.3) was sprayed under air in a spray tower according to the program. The hot air flow at the entrance had a temperature of 305 ° C, at the exit still 121 ° C. The dryer was operated with 450 kg / h of drying gas and 33 kg / h of nozzle gas (sputtering gas) with an atomization pressure of 3.5 bar.
Man erhielt ein gelbes gut rieselfähiges Pulver mit einer Restfeuchte von 8%. Es lag in Form von Partikeln vor, deren Durchmesser (D50) 8,5 μηη war. SEM-Bilder zeigten sphärische Ag- glomerate des gelben Pulvers, die im Inneren durch den organischen Bestandteil Laktose/Stärke zusammengehalten wurden. Schritt (b.3) A yellow free-flowing powder with a residual moisture content of 8% was obtained. It was in the form of particles whose diameter (D50) was 8.5 μηη. SEM images showed spherical agglomerates of the yellow powder held together by the organic component lactose / starch. Step (b.3)
60 g des wie vorstehend beschrieben erhaltenen gelben Pulvers wurden in einem 2-I- Quarzdrehkugelofen unter IS -Atmosphäre thermisch behandelt. Die 2-l-Quarzdrehkugel drehte sich mit einer Geschwindigkeit von 10 Umdrehungen/min. Zunächst erhitzte man innerhalb von 60 Minuten auf 700°C. Dann kalzinierte man 60 Minuten bei 700°C. Danach ließ man auf Zimmertemperatur abkühlen. Man siebte (mesh 50 μηη) und erhielt ein Elektrodenmaterial V-EM.3, welches schwarz aussah und pulverförmig anfiel. BET: 28 m2/g. Die Stampfdichte der Siebfraktion <32μηη betrug 0,81 g/ml. 60 g of the yellow powder obtained as described above was thermally treated in a 2 liter quartz rotary kiln under an atmosphere of IS. The 2 liter quartz spin ball rotated at a speed of 10 rpm. First, it was heated to 700 ° C within 60 minutes. Then calcined for 60 minutes at 700 ° C. Then allowed to cool to room temperature. It sieved (mesh 50 μηη) and received an electrode material V-EM.3, which looked black and was obtained in powder form. BET: 28 m 2 / g. The tamped density of the sieve fraction <32μηη was 0.81 g / ml.
I.4 Herstellung von Vergleichs-Elektrodenmaterial V-EM.4 I.4 Preparation of comparative electrode material V-EM.4
In Schritt (a.4) setzte man die folgenden Ausgangsmaterialien ein: In step (a.4), the following starting materials were used:
5,73 kg H3P03 (A.1 )5.73 kg H 3 P0 3 (A.1)
6,01 g LiOH ■ H20 (B.1 ) 6.01 g LiOH ■ H 2 O (B.1)
1 ,38 kg Laktose (C.1 ) 1, 38 kg lactose (C.1)
1 ,24 kg Stärke (C.3) 1, 24 kg of starch (C.3)
12,53 kg α-FeOOH (D2.1 ) Zuerst wurden 136 kg vollentsalztes Wasser in einem 200-Liter-Doppelmantelrührgefäß mit12.53 kg α-FeOOH (D2.1) First, 136 kg of demineralized water were placed in a 200 liter double-walled stirred vessel
Ankerrührer vorgelegt und auf 44°C aufgeheizt. Anschließend wurde das LiOH ■ H2O (B.1 ) darin gelöst und dann die Eisenverbindung (D2.1 ) zugegeben. Danach wurden Phosphorverbindungen (A.1 ) und (A.2) zugegeben. Die Temperatur stieg auf 62°C. Danach gab man die Kohlenstoffquellen (C.1 ) und (C.3) zu. Man rührte bei 70°C über einen Zeitraum von vierzehn Stunden nach (pH-Wert: 4,6). Man erhielt eine gelbe Suspension. Anchor stirrer submitted and heated to 44 ° C. Subsequently, the LiOH ■ H2O (B.1) was dissolved therein and then the iron compound (D2.1) was added. Thereafter, phosphorus compounds (A.1) and (A.2) were added. The temperature rose to 62 ° C. Thereafter, the carbon sources (C.1) and (C.3) were added. The mixture was stirred at 70 ° C. over a period of fourteen hours (pH: 4.6). A yellow suspension was obtained.
Trocknung desiccation
Die Lösung aus Schritt (a.4) wurde mit 4 I Wasser verdünnt und danach in einem Sprühturm nach Programm unter Luft versprüht. Der Heißluftstrom hatte beim Eingang eine Temperatur von 305°C, beim Ausgang noch 121 °C.  The solution from step (a.4) was diluted with 4 l of water and then sprayed in a spray tower under program in air. The hot air flow at the entrance had a temperature of 305 ° C, at the exit still 121 ° C.
Der Trockner wurde mit 450 kg/h Trocknungsgas betrieben sowie 33 kg/h Düsengas (Zerstäubungsgas) mit einem Zerstäubungsdruck von 3,5 bar.  The dryer was operated with 450 kg / h of drying gas and 33 kg / h of nozzle gas (sputtering gas) with an atomization pressure of 3.5 bar.
Man erhielt ein gelbes gut rieselfähiges Pulver mit einer Restfeuchte von 8%. Es lag in Form von Partikeln vor, deren Durchmesser (D50) 6,3 μηη und (D90) 19,4 μηη war. SEM-Bilder zeigten sphärische Agglomerate des gelben Pulvers, die im Inneren durch den organischen Bestandteil Stärke/Laktose zusammengehalten wurden. A yellow free-flowing powder with a residual moisture content of 8% was obtained. It was in the form of particles whose diameter (D50) was 6.3 μηη and (D90) 19.4 μηη. SEM images showed spherical agglomerates of the yellow powder held together by the organic component starch / lactose.
Schritt (b.4) Step (b.4)
60 g des wie vorstehend beschrieben erhaltenen gelben Pulvers wurden in einem 2-I- Quarzdrehkugelofen unter IS -Atmosphäre thermisch behandelt. Die 2-l-Quarzdrehkugel drehte sich mit einer Geschwindigkeit von 10 Umdrehungen/min. Zunächst erhitzte man innerhalb von 60 Minuten auf 700°C. Dann kalzinierte man 60 Minuten bei 700°C. Danach ließ man auf Zimmertemperatur abkühlen. Man siebte (mesh 50 μηη) und erhielt ein Elektrodenmaterial V-EM.4, welches schwarz aussah und pulverförmig mit bimodaler Partikelgrößenverteilung anfiel. BET: 9,1 m2/g. Die Stampfdichte der Siebfraktion <32μηη betrug 1 ,01 g/ml. 60 g of the yellow powder obtained as described above was thermally treated in a 2 liter quartz rotary kiln under an atmosphere of IS. The 2 liter quartz spin ball rotated at a speed of 10 rpm. First, you heated within 60 minutes at 700 ° C. Then calcined for 60 minutes at 700 ° C. Then allowed to cool to room temperature. It was sieved (mesh 50 μηη) and received an electrode material V-EM.4, which looked black and obtained in powder form with bimodal particle size distribution. BET: 9.1 m 2 / g. The tamped density of the sieve fraction <32μηη was 1, 01 g / ml.
I.5 Herstellung von Vergleichs-Elektrodenmaterial V-EM.5 I.5 Preparation of comparative electrode material V-EM.5
In Schritt (a.5) setzte man die folgenden Ausgangsmaterialien ein: In step (a.5), the following starting materials were used:
4,53 kg H3P03 (A.1 ) 4.53 kg H 3 P0 3 (A.1)
6,31 kg H3P04 (A.2) 6,31 kg H 3 P0 4 (A.2)
4,74 g LiOH ■ H20 (B.1 ) 4.74 g LiOH ■ H 2 O (B.1)
1 ,92 kg Polyvinylalkohol (C.4)  1, 92 kg polyvinyl alcohol (C.4)
12,53 kg α-FeOOH (D2.1 ) 12.53 kg α-FeOOH (D2.1)
Zuerst wurden 108 kg vollentsalztes Wasser in einem 200-Liter-Doppelmantelrührgefäß mit Ankerrührer vorgelegt und auf 47°C aufgeheizt. Anschließend wurde das LiOH ■ H2O (B.1 ) darin gelöst und dann die Eisenverbindung (D2.1 ) zugegeben. Danach wurden Phosphorverbindungen (A.1 ) und (A.2) zugegeben. Die Temperatur stieg auf 63°C. Danach gab man die Kohlenstoffquelle (C.4) zu. Man rührte bei 70°C über einen Zeitraum von vierzehn Stunden nach (pH- Wert: 4,5). Man erhielt eine gelbe Suspension. First, 108 kg of demineralized water were placed in a 200 liter double-walled stirred vessel equipped with anchor stirrer and heated to 47 ° C. Subsequently, the LiOH ■ H2O (B.1) was dissolved therein and then the iron compound (D2.1) was added. Thereafter, phosphorus compounds (A.1) and (A.2) were added. The temperature rose to 63 ° C. Thereafter, the carbon source (C.4) was added. The mixture was stirred at 70 ° C. over a period of fourteen hours (pH value: 4.5). A yellow suspension was obtained.
Trocknung desiccation
Der pH-Wert der Lösung aus Schritt (a.5) wurde mit Ammoniakwasser auf 5,0 eingestellt. Danach wurde die so erhaltene Lösung in einem Sprühturm nach Programm unter Luft versprüht. Der Heißluftstrom hatte beim Eingang eine Temperatur von 305°C, beim Ausgang noch 121 °C. Der Trockner wurde mit 450 kg/h Trocknungsgas betrieben sowie 33 kg/h Düsengas (Zerstäubungsgas) mit einem Zerstäubungsdruck von 3,5 bar.  The pH of the solution from step (a.5) was adjusted to 5.0 with ammonia water. Thereafter, the resulting solution was sprayed in a spray tower by program under air. The hot air flow at the entrance had a temperature of 305 ° C, at the exit still 121 ° C. The dryer was operated with 450 kg / h of drying gas and 33 kg / h of nozzle gas (sputtering gas) with an atomization pressure of 3.5 bar.
Man erhielt ein gelbes gut rieselfähiges Pulver mit einer Restfeuchte von 8%. Es lag in Form von Partikeln vor, deren Durchmesser (D50) 18,3 μηη war. SEM-Bilder zeigten sphärische Ag- glomerate des gelben Pulvers, die im Inneren durch den organischen Bestandteil Polyvinylalkohol zusammengehalten wurden. A yellow free-flowing powder with a residual moisture content of 8% was obtained. It was in the form of particles whose diameter (D50) was 18.3 μηη. SEM images showed spherical agglomerates of yellow powder held together by the organic component polyvinyl alcohol.
Schritt (b.5) 60 g des wie vorstehend beschrieben erhaltenen gelben Pulvers wurden in einem 2-I-Step (b.5) 60 g of the yellow powder obtained as described above were dissolved in a 2 l
Quarzdrehkugelofen unter IS -Atmosphäre thermisch behandelt. Die 2-l-Quarzdrehkugel drehte sich mit einer Geschwindigkeit von 10 Umdrehungen/min. Zunächst erhitzte man innerhalb von 60 Minuten auf 700°C. Dann kalzinierte man 60 Minuten bei 700°C. Danach ließ man auf Zimmertemperatur abkühlen. Man siebte (mesh 50 μηη) und erhielt ein Elektrodenmaterial V-EM.5, welches schwarz aussah und pulverförmig anfiel. BET: 8,9 m2/g. Die Stampfdichte der Siebfraktion <32μηη betrug 0,85 g/ml. 1.6 Herstellung von Vergleichs-Elektrodenmaterial V-EM.6 Quartz rotary kiln thermally treated under IS atmosphere. The 2 liter quartz spin ball rotated at a speed of 10 rpm. First, it was heated to 700 ° C within 60 minutes. Then calcined for 60 minutes at 700 ° C. Then allowed to cool to room temperature. One screened (mesh 50 μηη) and received an electrode material V-EM.5, which looked black and was obtained in powder form. BET: 8.9 m 2 / g. The tamped density of the sieve fraction <32μηη was 0.85 g / ml. 1.6 Preparation of comparative electrode material V-EM.6
In Schritt (a.6) setzte man die folgenden Ausgangsmaterialien ein:  In step (a.6), the following starting materials were used:
4,58 kg H3P03 (A.1 ) 4.58 kg H 3 P0 3 (A.1)
6.38 kg H3P04 (A.2) 6.38 kg H 3 P0 4 (A.2)
4,78 g LiOH ■ H20 (B.1 ) 4.78 g LiOH ■ H 2 O (B.1)
1 .39 kg Stearinsäure (C.5)  1 .39 kg of stearic acid (C.5)
9,81 kg α-FeOOH (D2.1 ) 9.81 kg α-FeOOH (D2.1)
Zuerst wurden 108 kg vollentsalztes Wasser in einem 200-Liter-Doppelmantelrührgefäß mit Ankerrührer vorgelegt und auf 47°C aufgeheizt. Anschließend wurde das LiOH ■ H2O (B.1 ) darin gelöst und dann die Eisenverbindung (D2.1 ) zugegeben. Danach wurden Phosphorverbindungen (A.1 ) und (A.2) zugegeben. Die Temperatur stieg auf 56°C. Danach gab man die Kohlenstoffquelle (C.5) zu. Man rührte bei 70°C über einen Zeitraum von vierzehn Stunden nach (pH- Wert: 4,5). Man erhielt eine gelbe Suspension. First, 108 kg of demineralized water were placed in a 200 liter double-walled stirred vessel equipped with anchor stirrer and heated to 47 ° C. Subsequently, the LiOH ■ H2O (B.1) was dissolved therein and then the iron compound (D2.1) was added. Thereafter, phosphorus compounds (A.1) and (A.2) were added. The temperature rose to 56 ° C. Thereafter, the carbon source (C.5) was added. The mixture was stirred at 70 ° C. over a period of fourteen hours (pH value: 4.5). A yellow suspension was obtained.
Trocknung desiccation
Man verdünnte die Lösung aus Schritt (a.6) mit 8 I Wasser. Danach wurde der pH-Wert der so verdünnten Lösung aus Schritt (a.6) mit Ammoniakwasser auf 5,0 eingestellt. Danach wurde die so erhaltene Lösung in einem Sprühturm nach Programm unter Luft versprüht. Der Heißluft- ström hatte beim Eingang eine Temperatur von 305°C, beim Ausgang noch 121 °C. Der Trockner wurde mit 450 kg/h Trocknungsgas betrieben sowie 33 kg/h Düsengas (Zerstäubungsgas) mit einem Zerstäubungsdruck von 3,5 bar.  The solution from step (a.6) was diluted with 8 l of water. Thereafter, the pH of the thus diluted solution from step (a.6) was adjusted to 5.0 with ammonia water. Thereafter, the resulting solution was sprayed in a spray tower by program under air. The hot air flow had a temperature of 305 ° C at the entrance, and 121 ° C at the exit. The dryer was operated with 450 kg / h of drying gas and 33 kg / h of nozzle gas (sputtering gas) with an atomization pressure of 3.5 bar.
Man erhielt ein gelbes gut rieselfähiges Pulver mit einer Restfeuchte von 8%. Es lag in Form von Partikeln vor, deren Durchmesser (D50) 14 μηη war. SEM-Bilder zeigten sphärische Agglomerate des gelben Pulvers, die im Inneren durch den organischen Bestandteil Stearinsäure zusammengehalten wurden. A yellow free-flowing powder with a residual moisture content of 8% was obtained. It was in the form of particles whose diameter (D50) was 14 μηη. SEM images showed spherical agglomerates of yellow powder held together by the organic component stearic acid.
Schritt (b.6) Step (b.6)
60 g des wie vorstehend beschrieben erhaltenen gelben Pulvers wurden in einem 2-I- Quarzdrehkugelofen unter IS -Atmosphäre thermisch behandelt. Die 2-l-Quarzdrehkugel drehte sich mit einer Geschwindigkeit von 10 Umdrehungen/min. Zunächst erhitzte man innerhalb von 60 Minuten auf 700°C. Dann kalzinierte man 60 Minuten bei 700°C. Danach ließ man auf Zim- mertemperatur abkühlen. Man siebte (mesh 50 μηη) und erhielt ein Elektrodenmaterial V-EM.6, welches hellgrau aussah und pulverförmig anfiel. BET: 4,1 m2/g. Die Stampfdichte der Siebfraktion <32μηη betrug 0,95 g/ml. 60 g of the yellow powder obtained as described above was thermally treated in a 2 liter quartz rotary kiln under an atmosphere of IS. The 2 liter quartz spin ball rotated at a speed of 10 rpm. First, it was heated to 700 ° C within 60 minutes. Then calcined for 60 minutes at 700 ° C. Thereafter, the mixture was allowed to cool to room temperature. One screened (mesh 50 μηη) and received an electrode material V-EM.6, which looked light gray and was obtained in powder form. BET: 4.1 m 2 / g. The tamped density of the sieve fraction <32μηη was 0.95 g / ml.
1.7 Herstellung von Vergleichs-Elektrodenmaterial V-EM.7 1.7 Preparation of comparative electrode material V-EM.7
In Schritt (a.7) setzte man die folgenden Ausgangsmaterialien ein: In step (a.7), the following starting materials were used:
4,53 kg H3P03 (A.1 ) 4.53 kg H 3 P0 3 (A.1)
6,31 kg H3P04 (A.2) 4,74 g LiOH ■ H20 (B.1 ) 6,31 kg H 3 P0 4 (A.2) 4.74 g LiOH ■ H 2 O (B.1)
1 .74 kg Laktose (C.1 )  1 .74 kg lactose (C.1)
1 .75 kg Mannitol (C.2)  1 .75 kg of mannitol (C.2)
9,71 kg α-FeOOH (D2.1 ) 9.71 kg α-FeOOH (D2.1)
Zuerst wurden 108 kg vollentsalztes Wasser in einem 200-Liter-Doppelmantelrührgefäß mit Ankerrührer vorgelegt und auf 43°C aufgeheizt. Anschließend wurde das LiOH ■ H2O (B.1 ) darin gelöst und dann die Eisenverbindung (D2.1 ) zugegeben. Danach wurden Phosphorverbindungen (A.1 ) und (A.2) zugegeben. Die Temperatur stieg auf 56°C. Danach gab man die Kohlen- stoffquellen (C.1 ) und (C.2) zu. Man rührte bei 70°C über einen Zeitraum von vierzehn Stunden nach (pH-Wert: 4,6). Man erhielt eine gelbe Suspension. First, 108 kg of demineralized water were placed in a 200 liter double-walled stirred vessel equipped with an anchor stirrer and heated to 43 ° C. Subsequently, the LiOH ■ H2O (B.1) was dissolved therein and then the iron compound (D2.1) was added. Thereafter, phosphorus compounds (A.1) and (A.2) were added. The temperature rose to 56 ° C. Thereafter, the carbon sources (C.1) and (C.2) were added. The mixture was stirred at 70 ° C. over a period of fourteen hours (pH: 4.6). A yellow suspension was obtained.
Trocknung desiccation
Man verdünnte die Lösung aus Schritt (a.7) mit 8 I Wasser. Danach wurde die so erhaltene Lösung in einem Sprühturm nach Programm unter Luft versprüht. Der Heißluftstrom hatte beim Eingang eine Temperatur von 305°C, beim Ausgang noch 121 °C. Der Trockner wurde mit 450 kg/h Trocknungsgas betrieben sowie 33 kg/h Düsengas (Zerstäubungsgas) mit einem Zerstäubungsdruck von 3,5 bar. Man erhielt ein gelbes gut rieselfähiges Pulver mit einer Restfeuchte von 8%. Es lag in Form von Partikeln vor, deren Durchmesser (D50) 15,8 μηη war. SEM-Bilder zeigten sphärische Agglomerate des gelben Pulvers, die im Inneren durch den organischen Bestandteil Lakto- se/Mannitol zusammengehalten wurden. Schritt (b.7)  The solution from step (a.7) was diluted with 8 l of water. Thereafter, the resulting solution was sprayed in a spray tower by program under air. The hot air flow at the entrance had a temperature of 305 ° C, at the exit still 121 ° C. The dryer was operated with 450 kg / h of drying gas and 33 kg / h of nozzle gas (sputtering gas) with an atomization pressure of 3.5 bar. A yellow free-flowing powder with a residual moisture content of 8% was obtained. It was in the form of particles whose diameter (D50) was 15.8 μηη. SEM images showed spherical agglomerates of the yellow powder held together internally by the organic component lactose / mannitol. Step (b.7)
60 g des wie vorstehend beschrieben erhaltenen gelben Pulvers wurden in einem 2-I- Quarzdrehkugelofen unter IS -Atmosphäre thermisch behandelt. Die 2-l-Quarzdrehkugel drehte sich mit einer Geschwindigkeit von 10 Umdrehungen/min. Zunächst erhitzte man innerhalb von 60 Minuten auf 700°C. Dann kalzinierte man 60 Minuten bei 700°C. Danach ließ man auf Zimmertemperatur abkühlen. Man siebte (mesh 50 μηη) und erhielt ein Elektrodenmaterial V-EM.7, welches schwarz aussah und pulverförmig anfiel. BET: 1 1 m2/g. Die Stampfdichte der Siebfraktion <32μηη betrug 1 ,1 1 g/ml. II. Herstellung von erfindungsgemäßen elektrochemischen Zellen 60 g of the yellow powder obtained as described above was thermally treated in a 2 liter quartz rotary kiln under an atmosphere of IS. The 2 liter quartz spin ball rotated at a speed of 10 rpm. First, it was heated to 700 ° C within 60 minutes. Then calcined for 60 minutes at 700 ° C. Then allowed to cool to room temperature. One screened (mesh 50 μηη) and received an electrode material V-EM.7, which looked black and was obtained in powder form. BET: 1 1 m 2 / g. The tamped density of the sieve fraction <32μηη was 1, 1 1 g / ml. II. Production of Electrochemical Cells According to the Invention
Erfindungsgemäßes Elektrodenmaterial wurde mit einem Bindemittel (iv.1 ): Copolymer von Vi- nylidenfluorid und Hexafluorpropen, als Pulver, kommerziell erhältlich als Kynar Flex® 2801 der Fa. Arkema, Inc., wie folgt verarbeitet. Zur Bestimmung der elektrochemischen Daten der Elektrodenmaterialien wurden 8 g erfindungsgemäßes Elektrodenmaterial aus Schritt EM.1 und 1 g (iv.1 ) unter Zusatz von 1 g N- Methylpyrrolidon (NMP) sowie 1 g Ruß zu einer Paste vermischt. Man beschichtet eine 30 μηη dicke Aluminiumfolie mit der vorstehend beschriebenen Paste (Aktivmaterialbeladung 4 mg/cm2). Nach Trocknung, aber ohne Kompression, bei 105°C wurden kreisförmige Teile der so beschichteten Aluminiumfolie (Durchmesser 20 mm) ausgestanzt. Aus den so erhältlichen Elektroden stellte man elektrochemische Zellen her. Inventive electrode material was processed with a binder (iv.1): copolymer of vinylidene fluoride and hexafluoropropene, as a powder, commercially available as Kynar Flex® 2801 from Arkema, Inc., as follows. To determine the electrochemical data of the electrode materials, 8 g of electrode material according to the invention from step EM.1 and 1 g (iv.1) with the addition of 1 g of N-methylpyrrolidone (NMP) and 1 g of carbon black were mixed to form a paste. It is coated a 30 μηη thick aluminum foil with the paste described above (active material loading 4 mg / cm 2 ). After drying, but without compression, at 105 ° C, circular parts of the thus coated aluminum foil (diameter 20 mm) were punched out. Electrochemical cells were prepared from the electrodes thus obtained.
Als Elektrolyt wurde eine 1 mol/l Lösung von LiPF6 in Ethylencarbonat/Dimethylcarbonat (1 :1 bezogen auf Massenanteile) eingesetzt. Die Anode der Testzellen bestand aus einer Lithiumfolie, die über einen Separator aus Glasfaserpapier zur Kathodenfolie in Kontakt steht. As the electrolyte, a 1 mol / l solution of LiPF6 in ethylene carbonate / dimethyl carbonate (1: 1 based on mass fractions) was used. The anode of the test cells consisted of a lithium foil, which is in contact with the cathode foil via a separator made of glass fiber paper.
Man erhält erfindungsgemäße elektrochemische Zellen EZ.1 . The invention gives electrochemical cells EZ.1.
Wenn man erfindungsgemäße elektrochemische Zellen zwischen 3 V und 4 V bei 25°C mit verschiedenen Raten (0.1 -6.5C, 1 C = 160 mAh/g) zyklisierte (laden/entladen), so zeigte sich bei hohen Entladeraten (6.5C) eine Steigerung der Kapazität, siehe Tabelle 1. Tabelle 1 : Entladegeschwindigkeiten bei hoher Kapazität When electrochemical cells according to the invention were cycled (charged / discharged) between 3 V and 4 V at 25 ° C. at different rates (0.1-6.5 C, 1 C = 160 mAh / g), high discharging rates (6.5 C) revealed a Capacity increase, see Table 1. Table 1: Discharge rates at high capacity
111.1 Herstellung von erfindungsgemäßem Elektrodenmaterial EM.8 111.1 Production of Inventive Electrode Material EM.8
In Schritt (a.8) setzte man die folgenden Ausgangsmaterialien ein: In step (a.8), the following starting materials were used:
29,10 g H3P03 (A.1 ) 29.10 g H 3 P0 3 (A.1)
39,42 g H3P04 (A.2) 39.42 g H 3 PO 4 (A.2)
29,99 g LiOH ■ H20 (B.1 ) 29.99 g of LiOH ■ H 2 O (B.1)
16,18 g Eisencitrat (D1 .1 )  16.18 g of iron citrate (D1 .1)
57,44 g α-FeOOH (D2.1 )  57.44 g of α-FeOOH (D2.1)
Zuerst wurden 165 g vollentsalztes Wasser bei RT vorgelegt. Anschließend wurde das LiOH ■ H2O (B.1 ) darin gelöst und dann die Eisenverbindungen (D1.1 ) und (D2.1 ) zugegeben. Danach wurden Phosphorverbindungen (A.1 ) und (A.2) zugegeben. Man rührte bei RT über einen Zeitraum von fünf Stunden nach. Man erhielt eine gelbe, homogene Suspensionslösung. Schritt (b.8) - Trocknung Die Lösung aus Schritt (a.1 ) wurde bei max. 85 °C und 10 mbar ca. 5 h eingeengt. Man erhielt eine klebrige, viskose, gelbe Masse. Diese wurde bei 95 °C ca. 12 h getrocknet. Es wurde ein gelbes Pulver erhalten Schritt (c.8) - Kalzinierung First, 165 g of demineralized water were initially charged at RT. Subsequently, the LiOH ■ H2O (B.1) was dissolved therein and then the iron compounds (D1.1) and (D2.1) was added. Thereafter, phosphorus compounds (A.1) and (A.2) were added. The mixture was stirred at RT for a period of five hours. A yellow, homogeneous suspension solution was obtained. Step (b.8) - Drying The solution from step (a.1) was diluted at max. Concentrated 85 ° C and 10 mbar for about 5 h. This gave a sticky, viscous, yellow mass. This was dried at 95 ° C for about 12 h. A yellow powder was obtained step (c.8) - calcination
60 g des wie vorstehend beschrieben erhaltenen Pulvers wurden in einem 2-I- Quarzdrehkugelofen unter IS -Atmosphäre thermisch behandelt. Die 2-l-Quarzdrehkugel drehte sich mit einer Geschwindigkeit von 10 Umdrehungen/min. Zunächst erhitzte man innerhalb von 60 Minuten auf 700°C. Dann kalzinierte man 60 Minuten bei 700°C. Danach ließ man auf Zim- mertemperatur abkühlen.  60 g of the powder obtained as described above were thermally treated in a 2 liter quartz rotary kiln under an atmosphere of IS. The 2 liter quartz spin ball rotated at a speed of 10 rpm. First, it was heated to 700 ° C within 60 minutes. Then calcined for 60 minutes at 700 ° C. Thereafter, the mixture was allowed to cool to room temperature.
Ein Teil des kalzinierten Materials wurde im Mörser zerkleinert und gesiebt (mesh 40 μηη). Man erhielt ein erfindungsgemäßes Elektrodenmaterial EM.8, welches schwarz aussah und pulver- förmig anfiel. EM.8 lässt sich ohne weiteres zu einer Paste niedriger Viskosität verarbeiten. Figur 1 zeigt eine rasterelektronen-mikroskopische Aufnahme des erhaltenen Elektrodenmaterials EM.8. Man erkennt ein feinteiliges homogenes Material.  Part of the calcined material was crushed in a mortar and sieved (mesh 40 μηη). This gave an inventive electrode material EM.8, which looked black and powdery incurred. EM.8 can easily be processed into a low viscosity paste. FIG. 1 shows a scanning electron micrograph of the resulting electrode material EM.8. One recognizes a finely divided homogeneous material.
III.2 Herstellung von Vergleichs-Elektrodenmaterial V-EM.9 In Schritt (a.9) setzte man die folgenden Ausgangsmaterialien ein: III.2 Preparation of Comparative Electrode Material V-EM.9 In step (a.9), the following starting materials were used:
29,32 g H3P03 (A.1 ) 29.32 g H 3 P0 3 (A.1)
39,45 g H3P04 (A.2) 39.45 g H 3 P0 4 (A.2)
30,02 g LiOH ■ H20 (B.1 ) 30.02 g LiOH ■ H 2 O (B.1)
16,15 g Eisencitrat (D1 .1 )  16.15 g of iron citrate (D1 .1)
57,33 g α-FeOOH (D2.1 ) 57.33 g of α-FeOOH (D2.1)
Zuerst wurden 140 g Ethanol bei RT vorgelegt. Anschließend wurde das LiOH ■ H2O (B.1 ) darin gelöst und dann die Eisenverbindungen (D1 .1 ) und (D2.1 ) zugegeben. Danach wurden Phosphorverbindungen (A.1 ) und (A.2) zugegeben. First, 140 g of ethanol were initially charged at RT. Subsequently, the LiOH ■ H2O (B.1) was dissolved therein and then the iron compounds (D1 .1) and (D2.1) was added. Thereafter, phosphorus compounds (A.1) and (A.2) were added.
Man rührte bei RT über einen Zeitraum von vier Stunden nach. Man erhielt eine gelbe, nicht homogene Suspensionslösung. Nach dem Versuch lagen in dem Reaktionsgemisch noch Partikel einer dunklen Substanz vor. Nach der zusätzlichen Zugabe von Ethanol hat sich das Versuchsbild nicht verändert. Das Reaktionsgemisch ist nicht homogen wie bei Herstellung von EM.8. The mixture was stirred at RT for a period of four hours. A yellow, non-homogeneous suspension solution was obtained. After the experiment, particles of a dark substance were still present in the reaction mixture. After the additional addition of ethanol, the experimental picture has not changed. The reaction mixture is not homogeneous as in the preparation of EM.8.
Schritt (b.9) - Trocknung Step (b.9) - Drying
Die Lösung aus Schritt (a.1 ) wurde bei max. 80 °C und bis 25 mbar ca. 5 h eingeengt. Man erhielt eine klebrige, gelbe Masse. Diese wurde im Umluft-Ofen bei 95°C über einen Zeitraum von 24 Stunden getrocknet. Es wurde ein gelbes Pulver erhalten. Schritt (c.9) - Kalzinierung  The solution from step (a.1) was diluted at max. Concentrated 80 ° C and 25 mbar for about 5 h. This gave a sticky, yellow mass. This was dried in a convection oven at 95 ° C over a period of 24 hours. A yellow powder was obtained. Step (c.9) - Calcination
60 g des wie vorstehend beschrieben Materials wurden in einem 2-l-Quarzdrehkugelofen unter N2-Atmosphäre thermisch behandelt. Die 2-l-Quarzdrehkugel drehte sich mit einer Geschwin- digkeit von 10 Umdrehungen/min. Zunächst erhitzte man innerhalb von 60 Minuten auf 700°C. Dann kalzinierte man 60 Minuten bei 700°C. Danach ließ man auf Zimmertemperatur abkühlen. 60 g of the material as described above were thermally treated in a 2 liter quartz rotary kiln under N 2 atmosphere. The 2-liter quartz spin ball rotated at a speed of speed of 10 revolutions / min. First, it was heated to 700 ° C within 60 minutes. Then calcined for 60 minutes at 700 ° C. Then allowed to cool to room temperature.
Ein Teil des kalzinierten Materials wurde im Mörser zerkleinert und gesiebt (mesh 40 μηη). Man erhielt das Elektrodenmaterial V-EM.9, welches schwarz aussah und pulverförmig anfiel. V- EM.9 lässt sich nicht zu einer homogenen Paste mit niedriger Viskosität weiterverarbeiten. Part of the calcined material was crushed in a mortar and sieved (mesh 40 μηη). The electrode material V-EM.9 was obtained, which looked black and was obtained in powder form. V-EM.9 can not be further processed into a homogeneous paste with low viscosity.
Figur 2 zeigt eine rasterelektronen-mikroskopische Aufnahme des Vergleichs- Elektrodenmaterials V-EM.9. Man erkennt ungleichmäßiges, zusammenhängendes Material grober Struktur. FIG. 2 shows a scanning electron micrograph of the comparative electrode material V-EM.9. One recognizes uneven, cohesive material of coarse structure.

Claims

Patentansprüche claims
1 . Verfahren zur Herstellung von Elektrodenmaterialien, dadurch gekennzeichnet, dass es die folgenden Schritte beinhaltet: 1 . Process for the production of electrode materials, characterized in that it comprises the following steps:
(a) man vermischt in Gegenwart von Wasser oder in Gegenwart von Wasser und organischem Lösungsmittel miteinander:  (a) mixing together in the presence of water or in the presence of water and organic solvent:
(A) mindestens eine Phosphorverbindung,  (A) at least one phosphorus compound,
(B) mindestens eine Lithiumverbindung,  (B) at least one lithium compound,
(C) mindestens eine Kohlenstoffquelle,  (C) at least one carbon source,
(D1 ) mindestens eine wasserlösliche Eisenverbindung, in der Fe in der Oxidations- stufe +2 oder +3 vorliegt,  (D1) at least one water-soluble iron compound in which Fe is in the oxidation state +2 or +3,
(D2) mindestens eine Eisenquelle, die von (D1 ) verschieden und wasserunlöslich ist und in der Fe in der Oxidationsstufe null, +2 oder +3 vorliegt,  (D2) at least one iron source which is different from (D1) and insoluble in water and in which Fe is in the oxidation state zero, +2 or +3,
(b) man behandelt die erhaltene Mischung thermisch.  (b) treating the resulting mixture thermally.
2. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass man die thermische Behandlung gemäß Schritt (b) bei 350 bis 1200°C durchführt. 2. The method according to claim 1, characterized in that one carries out the thermal treatment according to step (b) at 350 to 1200 ° C.
3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass man das in Schritt (a) eingesetzte Wasser ganz oder partiell entfernt. 3. The method according to claim 1 or 2, characterized in that one removes the water used in step (a) completely or partially.
4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass man mindestens zwei Phosphorverbindungen (A) einsetzt. 4. The method according to any one of claims 1 to 3, characterized in that one uses at least two phosphorus compounds (A).
5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass man mindestens zwei Kohlenstoffquellen (C) einsetzt. 5. The method according to any one of claims 1 to 4, characterized in that one uses at least two carbon sources (C).
6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass man was- serlösliche Eisenverbindung (D1 ) wählt aus Ammoniumeisencitrat, Eisenacetat, FeS04,6. The method according to any one of claims 1 to 5, characterized in that one selects water-soluble iron compound (D1) from ammonium iron citrate, iron acetate, FeS0 4 ,
Eisencitrat, Eisenlactat und Eisenchlorid. Iron citrate, iron lactate and ferric chloride.
7. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass man wasserunlösliche Eisenverbindung (D2) wählt aus Fe(OH)3, FeOOH , Fe2Ü3, Fe3Ü4, Eisen- phosphat, Eisenphosphonat und Eisencarbonat. 7. The method according to any one of claims 1 to 6, characterized in that water-insoluble iron compound (D2) selects Fe (OH) 3, FeOOH, Fe2Ü3, Fe3Ü 4, iron phosphate, iron carbonate and Eisenphosphonat.
8. Elektrodenmaterialien in partikulärer Form, enthaltend Agglomerate von Primärpartikeln, wobei die Agglomerate enthalten 8. Electrode materials in particulate form containing agglomerates of primary particles, which contain agglomerates
i. Primärpartikel von lithiiertem Eisenphosphat mit Olivinstruktur, wobei die Primärpar- tikel (i) einen mittleren Durchmesser (D50) im Bereich von 20 bis 250 nm aufweisen, ii. Primärpartikel von lithiiertem Eisenphosphat mit Olivinstruktur, wobei die Primärpartikel (ii) einen mittleren Durchmesser (D50) im Bereich von 300 bis 1000 nm aufweisen, i. Primary particles of lithiated iron phosphate having an olivine structure, the primary particles (i) having an average diameter (D50) in the range from 20 to 250 nm, ii. Primary particles of lithiated iron phosphate with olivine structure, wherein the primary particles (ii) have an average diameter (D50) in the range of 300 to 1000 nm,
iii. gegebenenfalls Kohlenstoff in elektrisch leitfähiger Modifikation.  iii. optionally carbon in electrically conductive modification.
9. Elektrodenmaterialien nach Anspruch 8, dadurch gekennzeichnet, dass Primärpartikel (i) und Primärpartikel (ii) in Agglomeraten in einem Volumenverhältnis (D50) im Bereich von 1 :9 bis 1 :1 vorliegen. 9. electrode materials according to claim 8, characterized in that primary particles (i) and primary particles (ii) in agglomerates in a volume ratio (D50) in the range of 1: 9 to 1: 1.
10. Elektrodenmaterialien nach Anspruch 8 oder 9, hergestellt nach einem Verfahren nach einem der Ansprüche 1 bis 7. 10. An electrode material according to claim 8 or 9, prepared by a method according to any one of claims 1 to 7.
1 1 . Verwendung von Elektrodenmaterialien nach einem der Ansprüche 8 bis 10 zur Herstellung von Elektroden von Lithium-Ionen-Batterien. 1 1. Use of electrode materials according to one of claims 8 to 10 for the production of electrodes of lithium-ion batteries.
12. Lithium-Ionen-Batterien, enthaltend mindestens eine Elektrode, enthaltend mindestens ein Elektrodenmaterial nach einem der Ansprüche 8 bis 10. 12. Lithium-ion batteries, containing at least one electrode, containing at least one electrode material according to one of claims 8 to 10.
13. Verwendung von Lithium-Ionen-Batterien nach Anspruch 12 in Vorrichtungen, die Batte- rien mit einer hohen Spitzenleistung erfordern. 13. The use of lithium-ion batteries according to claim 12 in devices which require batteries with a high peak power.
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